Field Portable X-ray Fluorescence Spectrometry Research Articles

Resampling with in situ field portable X-ray fluorescence spectrometry (FPXRF) to reduce the uncertainty in delineating the remediation area of soil heavy metals.

There must be some uncertainty in the remediation areas delineated based on limited sample points, and resampling in the high-uncertainty areas is particularly necessary. In situ field portable X-ray fluorescence spectrometry (FPXRF), a rapid and cheap analysis method for soil heavy metals, is strongly affected by many spatially non-stationary soil factors. This study first delineated the high-uncertainty area (threshold-exceeding probabilities (PTE) between 30% and 70%) of soil Pb based on the 1000 realizations produced by sequential Gaussian simulation (SGS) with 93 ICP-MS Pb concentrations measured in a peri-urban agriculture area, China. Next, in situ FPXRF was used to increase sample density in this high-uncertainty area. Then, robust geographically weighted regression (RGWR) was used to correct the in situ FPXRF Pb, and the correction accuracies of RGWR, basic GWR, and traditionally-used ordinary least squares regression (OLSR) were compared. Finally, to explore the best way to combine these corrected in situ FPXRF concentrations in delineating the remediation area, we compared the following spatial simulation methods: basic SGS, sequential Gaussian co-simulation (CoSGS) with the RGWR-corrected in situ FPXRF Pb as auxiliary soft data (CoSGS-CorFPXRF), and SGS with the RGWR-corrected in situ FPXRF Pb as part of hard data (SGS-CorFPXRF). Results showed that (i) RGWR produced higher correction accuracy (RI=71.5%) than GWR (RI=59.68%) and OLSR (RI=25.58%) for the in situ FPXRF Pb; (ii) SGS-CorFPXRF produced less uncertainty (G=0.97) than CoSGS-CorFPXRF (G=0.95) and SGS (G=0.91) in the spatial simulation; (iii) High-uncertainty area (30%<PTE<70%) was reduced from 36.55% to 8.7% of the whole study area. It is concluded that the recommended methods are cost-effective to reduce the uncertainty in delineating the remediation areas of soil heavy metals.

Source apportionment of soil heavy metals using robust spatial receptor model with categorical land-use types and RGWR-corrected in-situ FPXRF data.

High-density samples are usually a prerequisite for obtaining high-precision source apportionment results in large-scale areas. In-situ field portable X-ray fluorescence spectrometry (FPXRF) is a fast and cheap way to increase the sample size of soil heavy metals (HMs). Moreover, categorical land-use types may be closely associated with source contributions. However, the above information has rarely been incorporated into the source apportionment. In this study, robust geographically weighted regression (RGWR) was first used to correct the spatially varying effect of the related soil factors (e.g., soil water and soil organic matter) on in-situ FPXRF in an urban-rural fringe of Wuhan City, China, and the correction accuracy of RGWR was compared with those of the traditionally non-spatial multiple linear regression (MLR) and basic GWR. Then, the effect of land-use types on HM concentrations was partitioned using analysis of variance (ANOVA). Last, based on the robust spatial receptor model (i.e., robust absolute principal component scores/RGWR [RAPCS/RGWR]), this study proposed RAPCS/RGWR with categorical land-use types and RGWR-corrected in-situ FPXRF data (RAPCS/RGWR_LU&FPXRF), and its performance was compared with those of RAPCS/RGWR with none or one kind of auxiliary data. Results showed that (i) the performances of the correction models for in-situ FPXRF data were in the order of RGWR>GWR>MLR, and the relative improvement of RGWR over MLR ranged from 52.6% to 70.71% for each HM; (ii) categorical land-use types significantly affected the concentrations of soil Zn, Cu, As, and Pb; (iii) the highest estimation accuracy for source contributions was obtained by RAPCS/RGWR_LU&FPXRF, and the lowest estimation accuracy was obtained by basic RAPCS/RGWR. It is concluded that land-use types and RGWR-corrected in-situ FPXRF data are closely associated with the source contribution, and RAPCS/RGWR_LU&FPXRF is a cost-effective source apportionment method for soil HMs in large-scale areas.

Biogeochemical mapping of metal contamination from mine tailings using field-portable XRF

Trace and major element composition of selected plant species and parts may be used to map geochemical dispersion from mineral deposits and contaminated areas. This study examines the application of field-portable X-ray fluorescence spectrometry (fpXRF) in obtaining real-time biogeochemical data. In situ analysis of parts of black and silver wattle (Acacia mearnsii De Wild. and Acacia dealbata Link) was conducted to map the extent of contamination surrounding the former Woodlawn base metal mine. High levels of ore-related elements were detected in the bark of these species in a zone extending up to 1 km down-drainage from the tailing ponds. Major elements are more elevated in bark on the side of the trees facing the tailings ponds and correlations between trace and major elements indicate dust contamination. The penetration distance for X-rays is dependent on the energy of the secondary X-rays measured, with the maximum depth of penetration in bark and leaf material <30 mm. There was a close correlation for most elements between the fpXRF and laboratory-based XRF analysis but with element-dependent attenuation by the organic matrix. Providing there is consistency in sampling and analytical methodology, in situ fpXRF analysis of vegetation is an effective method in both contamination surveys and biogeochemical mineral exploration for a range of trace and major elements.

Applicability of a field portable X-ray fluorescence for analyzing elemental concentration of waste samples

Determining the chemical properties of waste is crucial to ensure the most effective utilization of waste. The standard laboratory measurements can produce accurate results, but analysis is labor- and time-consuming. The variety of elements that field portable X-ray fluorescence spectrometry (FPXRF) can detect from selected waste materials was studied, including how the results compared with those of inductively coupled plasma mass spectrometry (ICP-MS) measurements. The selected materials were fine fraction reject from solid recovered fuel production, fly ash, biowaste, and compost. Based on the results, FPXRF is reported to be best suited for waste samples, such as ash and compost, because of their physical properties, as follows: not too moist, quite small particle size, and not too heterogeneous. The results obtained from FPXRF showed the lowest relative standard deviation for ash material. The analysis of the limits of agreement between FPXRF and ICP-MS showed that FPXRF was mainly suitable for qualitative assessment. Furthermore, regression analysis showed a linear correlation between FPXRF and ICP-MS results for calcium and zinc in the selected materials. Keeping the limitations in mind, FPXRF could be used for qualitative analysis in waste treatment processes, such as first quality control of waste materials.

Rapid evaluation of arsenic contamination in paddy soils using field portable X-ray fluorescence spectrometry

Arsenic (As) in paddy fields is deteriorating food security and human health through rice ingestion. Rice is the dominant food source of arsenic exposure to half of the world's population. Therefore, an in situ effective method for As risk evaluation in paddy soil is strongly needed to avoid As exposure through rice ingestion. Herein, we developed a rapid analytical methodology for determination of As in plant tissues using field portable X-ray fluorescence spectrometry (FP-XRF). This method was applied to rice roots in order to evaluate the As contamination in paddy soils. The results showed that rice roots with iron plaques were superior to rhizosphere soils for generating FP-XRF signals, especially for field sites with As concentrations lower than the soil detection limit of FP-XRF (30.0mg/kg). Moreover, the strong linear relationships of As concentrations between the rice roots and corresponding leaves and grains proved that the rice root, rather than the soil, is a better predictor of As concentrations in rice grains. The research provides an efficient As monitoring method for As contaminated paddy fields by using wetland plant roots with iron plaques and XRF-based analytical techniques.

Geochemical exploration for vertebrate fossils using field portable XRF

The Riversleigh World Heritage Area in Queensland contains a vast array of Oligocene-Pleistocene vertebrate, invertebrate and plant fossils. The existing suite of fossil deposits contains a number of temporal gaps in the faunal succession, and exploration is turning to large expanses of recently-discovered Cenozoic carbonates to the west and south of Riversleigh. Previous exploration for new deposits has been primarily based on visual detection of bone or tooth fragments in outcrops or by excavation of sites where lithofacies or mineralogy indicates potential host structures. This study examines the application of field-portable X-ray fluorescence spectrometry (fpXRF) to detecting lithogeochemical or mineralogical indicators of fossil fragments and host structures where visual indicators are absent or subtle. Elemental analysis of outcrops by fpXRF has permitted geochemical differentiation of Cenozoic from underlying Cambrian limestones using Sr/Ca and Mn/Ca ratios. Potentially productive depositional environments and structures such as caves and palaeo-channels can be mapped using various combinations of Ti, Zr, and other relatively immobile elements associated with heavy minerals. Detection of finely-divided vertebrate fossiliferous materials is also possible, using ratios of U, Zn and Pb against Ca, or simply by detecting elevated P. The provision of real-time lithogeochemical data by fpXRF offers potential to accelerate the current exploration program in the Riversleigh area, at regional to local scales, and the detection of important vertebrate fossil deposits otherwise overlooked using the conventional visual survey methods.

Lead in exterior paints from the urban and suburban environs of Plymouth, south west England

Dry weight concentrations of lead in paints on a variety of structures in the urban and suburban environs of a British city (Plymouth, south west England) were determined in situ and ex situ by field-portable X-ray fluorescence spectrometry. Lead was detected in 221 out of 272 analyses, with overall median and mean concentrations of 4180μgg−1 and 29,300μgg−1, respectively, and a maximum concentration of 390,000μgg−1. Highest concentrations were observed in extant paints on poorly maintained, metallic structures, including railings, gates, telephone kiosks and bridges, in various yellow road line paints, and in paints of varying condition on public playground facilities (ramps, climbing frames, monkey bars). Occupants of households in the vicinity of structures that are shedding leaded paint are at potential risk of exposure from paint particles being tracked in on shoes and clothing while children in contact with leaded paints in playgrounds and recreational areas are at potential risk from the direct ingestion of paint flakes. Since the issues highlighted in the present study are neither likely to be restricted to this city, nor to the UK, a greater, general awareness and understanding of the sources and routes of exposure of exterior leaded paint is called for.

Field-portable X-ray fluorescence spectrometry as rapid measurement tool for landfill mining operations: comparison of field data vs. laboratory analysis

Landfill mining applied in reclamation at the territories of old dump sites and landfills is a known approach tended to global economic and environmental benefits as recovery of metals and energy is an important challenge. The aim of this study was to analyse the concentration of several metallic elements (Ca, Cu, Cr, Fe, K, Mn, Pb, Zn) in the fine fraction of waste derived in the landfill and to compare the results of measurements obtained by field-portable equipment with the data gained by advanced analytical tools. Atomic absorption spectrometry (AAS) and inductively coupled plasma mass spectrometry (ICP-MS) were used for the quantitative detection of metallic elements at the laboratory; whereas field-portable X-ray fluorescence spectrometry (FPXRF) was applied for rapid sample characterisation in the field (on-site). Wet digestion of samples (fine fraction of waste at landfill) was done prior analytical procedures at the laboratory conditions, but FPXRF analysis was performed using raw solid samples of waste fine fraction derived in the Kudjape Landfill in Estonia. Although the use of AAS and ICP-MS for the measurements of metals achieves more precise results, it was concluded that precision and accuracy of the measurements obtained by FPXRF is acceptable for fast approximate evaluation of quantities of metallic elements in fine fraction samples excavated from the waste at landfills. Precision and accuracy of the results provided by express method is acceptable for quick analysis or screening of the concentration of major and trace metallic elements in field projects; however, data correction can be applied by calculating moisture and organic matter content dependent on sample matrix as well as special attention must be paid on sample selection and homogenisation and number of analysed samples.

Evaluation of Field Portable X-Ray Fluorescence Performance for the Analysis of Ni in Soil.

As a rapid, in-situ analysis method, Field portable X-ray fluorescence spectrometry (FP-XRF) can be widely applied in soil heavy metals analysis field. Whereas, some factors may affect FP-XRF performance and restrict the application. Studies have proved that FP-XRF has poorer performance when the concentration of target element is low, and soil moisture and particle size will affect FP-XRF performance. But few studies have been conducted in depth. This study took an example of Ni, demonstrated the relationship between Ni concentration and FP-XRF performance on accuracy and precision, and gave a critical value. Effects of soil moisture and particle size on accuracy and precision also had been compared. Results show that, FP-XRF performance is related to Ni concentration and the critical value is 400 mg x kg(-1). Relative standard deviation (RSD) and relative uncertainty decrease while the Ni concentration is below 400 mg x kg(-1), hence FP-XRF performance improves with increasing Ni concentration in this range; RSD and relative uncertainty change little while the Ni concentration is above 400 mg x kg(-1), hence FP-XRF performance does not have correlation with Ni concentration any more. For in-situ analysis, the relative uncertainty contributed by soil moisture is 3.77%, and the relative certainty contributed by particle size is 0.56%. Effect of soil moisture is evidently more serious than particle size both on accuracy and precision.

Assessment of field portable X-ray fluorescence spectrometry for the in situ determination of heavy metals in soils and plants

In soil pollution studies, large numbers of soil samples collected at random need to be processed and analyzed to determine their heavy metal contents. This study was designed to assess the use of a field portable X-ray fluorescence (FPXRF) spectrometry system for the in situ determination of heavy metal levels in both soil and plant samples. First, we optimised the method using 84 reference soil standards and soil samples from known polluted sites. The optimised method was then used to determine heavy metals at three abandoned mine sites and two sealed landfills in central Spain. Given that knowledge of heavy metal levels in plants is important for the ecotoxicological study of these sites, the FPXRF device was also used to determine heavy metals in plants. Our results indicate the acceptable to high quality of the data provided by the system especially for soil samples. The cost-benefits and sustainability of this instrument in relation to other techniques were also examined. The use of the FPXRF system for the study of potentially polluted sites was found to save on costs, time and materials. Results indicate its suitable use for the preliminary screening of heavy-metal polluted sites.

Quantification of trace arsenic in soils by field-portable X-ray fluorescence spectrometry: Considerations for sample preparation and measurement conditions

Recent technological improvements have led to the widespread adoption of field portable energy dispersive X-ray fluorescence (FP-XRF) by governmental agencies, environmental consultancies and research institutions. FP-XRF units often include analysis modes specifically designed for the quantification of trace elements in soils. Using these modes, X-ray tube based FP-XRF units can offer almost “point and shoot” ease of use and results comparable to those of laboratory based instruments. Nevertheless, FP-XRF analysis is sensitive to spectral interferences as well as physical and chemical matrix effects which can result in decreased precision and accuracy. In this study, an X-ray tube-based FP-XRF analyser was used to determine trace (low ppm) concentrations of As in a floodplain soil. The effect of different sample preparation and analysis conditions on precision and accuracy were systematically evaluated. We propose strategies to minimise sources of error and maximise data precision and accuracy, achieving in situ limits of detection and precision of 6.8ppm and 14.4%RSD, respectively for arsenic. We demonstrate that soil moisture, even in relatively dry soils, dramatically affects analytical performance with a signal loss of 37% recorded for arsenic at 20wt% soil moisture relative to dry soil. We also highlight the importance of the use of certified reference materials and independent measurement methods to ensure accurate correction of field values.

Applicability of hyperspectral technology for in situ phytoremediation

The characterization of heavy metal polluted abandoned mining sites is a complicated assignment due to the variable spatial distribution of the pollutants, therefore complex integrated method is required in order to assess precisely the amount and the distribution of the contaminants. The examined area is flotation sludge reservoir of abandoned Pb-Zn mining site with serious heavy metal contamination. located in Gyöngyösoroszi, Northern Hungary.The hyperspectral image of the flotation sludge is obtained by using a Digital Airborne Imaging Spectrometer DAIS 7915, in the frame of DLR HySens first Hungarian hyperspectral flight campaign (21/08/2002). Parallel to the flight campaign heavy metal content of soil samples were examined from the area of the flotation sludge. The analysis of hyperspectral data was verified by the examination of mine tailing samples by FPXRF (Field Portable X-ray Fluorescence spectrometry) (NITON XL-703).Determinations of heavy metal containing minerals are based on the spectral profiles of the pixels of the area with using USGIS standard spectral profiles of the examined materials (galena, pyrite, sphalerite, goethite and jarosit).&#x0D; Applying the Spectral Angle Mapper with BandMax classification the distribution of minerals (galena, pyrite, sphalerite, goethite, jarosit) in the area was defined. The mineral formation occurs especially at the levees and the barren places of the Szárazvölgyi flotation sludge reservoir. Based on the statistic results of the samples, principal component analysis and correlation coefficient between the different metal content of the samples were calculated. The highest correlations were found between Pb-Zn, Fe-Zn and between Fe-Pb. This prove the results of the principal component analysis, where usually Pb, Zn, Fe introduce the main component.&#x0D; Canopy analysis was also carried out with the hyperspectal image in order to classify the differences between vegetation types at the Szárazvölgy flotation sludge reservoir and analyse the applicability of it. Supervised classification methods were used to distinguish 8 vegetation types based on the spectral properties of the area. The results of the classifications were compared to a ground truth image, based on ortophoto, topographic map, and GPS based field data collection. According to results of the comparison, the paralellpiped classification method is proved to be appropriate method based on the overall accuracy of canopy classification, which was 54% due to heterogeneity of the vegetation. &#x0D; The results of hyperspectral data and FPXRF analysis suggest that Pb, Zn and Fe containing minerals have similar spatial distribution in the examined and barren area.&#x0D; Based on this study hyperspectral remote sensing is likely to be an effective tool for the characterization and modeling the distribution of Pb, Zn and Fe containing minerals at the examined heavy metal polluted sites. Further more, based on the vegetation analysis plant species for phytoremediation can be defined.

Field-portable X-ray fluorescence spectrometry for metals in marine sediments: results from multiple sites

The two goals of this study were to (i) test the capabilities of the portable instrument relative to detailed standard chemical analyses, and (ii) evaluate instrument response at multiple sediment sites. Results from FPXRF analyses of sediment samples from various locations have been compared with results from standard analyses (ICP, AAS, Laboratory XRF). The data are used to draw correlations between the different methods, and evaluate the universality of the instrument. The ability to reliably detect metals in sediments allows for the generation of data from sediment grabs in a time frame short enough to guide on site decision-making for mapping strategies and detailed sampling.

Field-portable X-ray Fluorescence Spectrometry for metals in marine sediments: Results from multiple sites

The two goals of this study were to (i) test the capabilities of the portable instrument relative to detailed standard chemical analyses, and (ii) evaluate instrument response at multiple sediment sites. Results from FPXRF analyses of sediment samples from various locations have been compared with results from standard analyses (ICP, AAS, Laboratory XRF). The data are used to draw correlations between the different methods, and evaluate the universality of the instrument. The ability to reliably detect metals in sediments allows for the generation of data from sediment grabs in a time frame short enough to guide on site decision-making for mapping strategies and detailed sampling.

Field-portable X-ray fluorescence spectrometry: Past, present, and future

The method of X-ray fluorescence (XRF) spectrometry, one of the oldest instrumental methods of analysis, dates its origins to the beginning of this century. The method has gone through many significant changes since then, including the advent of field-portable systems 30 years ago. The desire to bring the instrument to the field to perform sample analysis, rather than in the laboratory, is not new. On-site analysis is better for many reasons, most of which are economical; however, it was also for these same economical reasons that it could not be realized. Either the instruments simply could not function in the field, or they were prohibitively expensive. Ongoing technology developments, particularly recent ones in computer microchip and detector technology, has led to the design and production of battery-operated, field-portable X-ray analyzers. This led to a new analytical method, field-portable X-ray fluorescence (FPXRF). This method uses instruments that can routinely achieve analytical performance equal to that of conventional laboratory systems. The ever-increasing power of computers, and their miniaturization, permits packing more complex and powerful software into portable instruments. This trend will lead to instruments that will provide solutions and decisions rather than just analytical results. We will follow the development of the FPXRF analyzers from their origin and illustrate their analytical performance in typical applications. © 1997 John Wiley & Sons, Inc. Field Analyt Chem Technol 1: 317–329, 1997