David C. Weindorf

Use of portable X-ray fluorescence spectrometry for environmental quality assessment of peri-urban agriculture

Urban expansion into traditional agricultural lands has augmented the potential for heavy metal contamination of soils. This study examined the utility of field portable X-ray fluorescence (PXRF) spectrometry for evaluating the environmental quality of sugarcane fields near two industrial complexes in Louisiana, USA. Results indicated that PXRF provided quality results of heavy metal levels comparable to traditional laboratory analysis. When coupled with global positioning system technology, the use of PXRF allows for on-site interpolation of heavy metal levels in a matter of minutes. Field portable XRF was shown to be an effective tool for rapid assessment of heavy metals in soils of peri-urban agricultural areas.

Chapter One – Advances in Portable X-ray Fluorescence (PXRF) for Environmental, Pedological, and Agronomic Applications

Abstract Contemporary soil, agronomic, and environmental investigations require high quality data for the development of sound management decisions. For years, X-ray fluorescence (XRF) spectrometry has been known to provide accurate elemental data in a wide range of matrices. However, advances in the past two decades have now made the technology portable. Improvements to spectrometer design have led to the replacement of many active source X-ray units with X-ray tubes that only emit X-rays when energized. Several generations of detector improvement have resulted in the current standard for many units, the silicon drift detector, which is capable of much lower limits of detection than its predecessors. Field portable X-ray fluorescence (PXRF) spectrometers offer many advantages over traditional techniques including speed, portability, wide dynamic range of elemental quantification, little/no need for sample pretreatment, and simplicity. Furthermore, PXRF analyses are nondestructive, allowing for analyzed samples to be preserved for future use. This review presents an overview of the development, operational theory, and contemporary uses of PXRF. Also, benefits and limitations to PXRF use are presented. Many industrial uses are covered, but deference is paid to rapidly advancing environmental, pedological, and agronomic applications of PXRF. Summarily, PXRF offers a range of benefits not possible with traditional laboratory techniques.

In-situ assessment of metal contamination via portable X-ray fluorescence spectroscopy: Zlatna, Romania

Zlatna, Romania is the site of longtime mining/smelting operations which have resulted in widespread metal pollution of the entire area. Previous studies have documented the contamination using traditional methods involving soil sample collection, digestion, and quantification via inductively coupled plasma atomic emission spectroscopy or atomic absorption. However, field portable X-ray fluorescence spectroscopy (PXRF) can accurately quantify contamination in-situ, in seconds. A PXRF spectrometer was used to scan 69 soil samples in Zlatna across multiple land use types. Each site was georeferenced with data inputted into a geographic information system for high resolution spatial interpolations. These models were laid over contemporary aerial imagery to evaluate the extent of pollution on an individual elemental basis. Pb, As, Co, Cu, and Cd exceeded governmental action limits in >50% of the sites scanned. The use of georeferenced PXRF data offers a powerful new tool for in-situ assessment of contaminated soils.

Spatial Variability of Soil Properties at Capulin Volcano, New Mexico, USA: Implications for Sampling Strategy

Abstract Non-agricultural lands are surveyed sparsely in general. Meanwhile, soils in these areas usually exhibit strong spatial variability which requires more samples for producing acceptable estimates. Capulin Volcano National Monument, as a typical sparsely-surveyed area, was chosen to assess spatial variability of a variety of soil properties, and furthermore, to investigate its implications for sampling design. One hundred and forty one composited soil samples were collected across the Monument and the surrounding areas. Soil properties including pH, organic matter content, extractable elements such as calcium (Ca), magnesium (Mg), potassium (K), sodium (Na), phosphorus (P), sulfur (S), zinc (Zn), and copper (Cu), as well as sand, silt, and clay percentages were analyzed for each sample. Semivariograms of all properties were constructed, standardized, and compared to estimate the spatial variability of the soil properties in the area. Based on the similarity among standardized semivariograms, we found that the semivariograms could be generalized for physical and chemical properties, respectively. The generalized semivariogram for physical properties had a much greater sill value (2.635) and effective range (7 500 m) than that for chemical properties. Optimal sampling density (OSD), which is derived from the generalized semivariogram and defines the relationship between sampling density and expected error percentage, was proposed to represent, interpret, and compare soil spatial variability and to provide guidance for sample scheme design. OSDs showed that chemical properties exhibit a stronger local spatial variability than soil texture parameters, implying more samples or analysis are required to achieve a similar level of precision.

Evaluation of Portable X-ray Fluorescence for Gypsum Quantification in Soils

The use of field portable X-ray fluorescence (XRF) spectrometry as a quantification tool for gypsum content in soils of West Texas and southern New Mexico, USA, was evaluated. Six sites were evaluated with gypsum contents ranging from less than 10% to greater than 90%. Samples collected from each site were scanned in the field using XRF and then transported to the laboratory for additional XRF scanning. Variables that might affect XRF scanning results, such as scanning time, particle size, moisture content, and so on, were evaluated. Both gypsum (CaSO4 • 2H2O) and calcite (CaCO3) were quantified using standard laboratory techniques. Three data sets were compared: (1) soil characterization data, obtained from the National Soil Survey Laboratory Research Database in Lincoln, NE; (2) quantitative X-ray diffraction; and (3) portable XRF (PXRF). The best correlation of gypsum XRF data (via Ca quantification minus calcite content) and laboratory data was between PXRF and quantitative X-ray diffraction (R = 0.96). On average, PXRF provided results within 6% of soil characterization data, the current laboratory standard for gypsum quantification. Field PXRF shows considerable promise as a rapid, quantifiable measure of gypsum in soils.

Determination of soil calcium using field portable X-ray fluorescence.

Soil calcium (Ca) determines several characteristics of soil fertility and affects many plant functions after absorption. It is necessary to develop a method to quickly determine soil Ca content in situ because soil Ca content can vary considerably in natural environments. Laboratory determination of Ca is laborious and costly. This study assessed the potential of field portable X-ray fluorescence (FPXRF) to be used in soil Ca determination. The consistency, repeatability, and accuracy of FPXRF are carefully examined using both artificial and natural soil samples. The effects of sample treatments including drying, bagging, grinding, and sieving on FPXRF are also investigated. Results show that FPXRF can detect and quantify total soil Ca content rapidly, accurately, and consistently with standard or specific calibration.

Development of a hybrid proximal sensing method for rapid identification of petroleum contaminated soils.

UNLABELLED Using 108 petroleum contaminated soil samples, this pilot study proposed a new analytical approach of combining visible near-infrared diffuse reflectance spectroscopy (VisNIR DRS) and portable X-ray fluorescence spectrometry (PXRF) for rapid and improved quantification of soil petroleum contamination. Results indicated that an advanced fused model where VisNIR DRS spectra-based penalized spline regression (PSR) was used to predict total petroleum hydrocarbon followed by PXRF elemental data-based random forest regression was used to model the PSR residuals, it outperformed (R(2)=0.78, residual prediction deviation (RPD)=2.19) all other models tested, even producing better generalization than using VisNIR DRS alone (RPDs of 1.64, 1.86, and 1.96 for random forest, penalized spline regression, and partial least squares regression, respectively). Additionally, unsupervised principal component analysis using the PXRF+VisNIR DRS system qualitatively separated contaminated soils from control samples. CAPSULE Fusion of PXRF elemental data and VisNIR derivative spectra produced an optimized model for total petroleum hydrocarbon quantification in soils.

Assessing the risks of trace elements in environmental materials under selected greenhouse vegetable production systems of China

The risk assessment of trace elements of different environmental media in conventional and organic greenhouse vegetable production systems (CGVPS and OGVPS) can reveal the influence of different farming philosophy on the trace element accumulations and their effects on human health. These provide important basic data for the environmental protection and human health. This paper presents trace element accumulation characteristics of different land uses; reveals the difference of soil trace element accumulation both with and without consideration of background levels; compares the trace element uptake by main vegetables; and assesses the trace element risks of soils, vegetables, waters and agricultural inputs, using two selected greenhouse vegetable systems in Nanjing, China as examples. Results showed that greenhouse vegetable fields contained significant accumulations of Zn in CGVPS relative to rice-wheat rotation fields, open vegetable fields, and geochemical background levels, and this was the case for organic matter in OGVPS. The comparative analysis of the soil medium in two systems with consideration of geochemical background levels and evaluation of the geo-accumulation pollution index achieved a more reasonable comparison and accurate assessment relative to the direct comparison analysis and the evaluation of the Nemerow pollution index, respectively. According to the Chinese food safety standards and the value of the target hazard quotient or hazard index, trace element contents of vegetables were safe for local residents in both systems. However, the spatial distribution of the estimated hazard index for producers still presented certain specific hotspots which may cause potential risk for human health in CGVPS. The water was mainly influenced by nitrogen, especially for CGVPS, while the potential risk of Cd and Cu pollution came from sediments in OGVPS. The main inputs for trace elements were fertilizers which were relatively safe based on relevant standards; but excess application caused trace element accumulations in the environmental media.

Metals analysis of agricultural soils via portable X-ray fluorescence spectrometry.

To assess the applicability of portable X-ray fluorescence (PXRF) spectrometry for metals analysis, total concentrations of As, Pb, Cu, and Zn in 47 agricultural soils were determined using in situ PXRF analysis, ex situ PXRF analysis, and conventional laboratory analysis. The correlation regression parameters of PXRF data with the data of conventional analysis were significantly improved upon going from in situ to ex situ, indicating that improvement of the ex situ PXRF data quality was achieved thorough sample preparation. Use of PXRF in situ was inferior to other analyses, especially when attempting to quantify relatively low levels of metals in agricultural soils. A high degree of linearity and similar spatial distribution existed between ex situ PXRF and laboratory analysis, suggesting that PXRF can be used in rapid detection or screening of agricultural soils, but is best followed with additional sample preparation ex situ and laboratory confirmation.

Scale Effect of Climate and Soil Texture on Soil Organic Carbon in the Uplands of Northeast China

Abstract Understanding how spatial scale influences commonly-observed effects of climate and soil texture on soil organic carbon (SOC) storage is important for accurately estimating the SOC pool at different scales. The relationships among climate factors, soil texture and SOC density at the regional, provincial, city, and county scales were evaluated at both the soil surface (0–20 cm) and throughout the soil profile (0–100 cm) in the Northeast China uplands. We examined 1 022 profiles obtained from the Second National Soil Survey of China. The results indicated that the relationships between climate factors and SOC density generally weakened with decreasing spatial scale. The provincial scale was optimal to assess the relationship between climate factors and SOC density because regional differences among provinces were covered up at the regional scale. However, the relationship between soil texture and SOC density had no obvious trend with increasing scale and changed with temperature. There were great differences in the impacts of climate factors and soil texture on SOC density at different scales. Climate factors had a larger effect on SOC density than soil texture at the regional scale. Similar trends were seen in Heilongjiang and eastern Inner Mongolia at the provincial scale. But, soil texture had a greater effect on SOC density compared with climate factors in Jilin and Liaoning. At the city and county scales, the influence of soil texture on SOC density was more important than climate factors.