This review covers developments in the analysis of chemicals, metals and functional materials. We have strengthened the criticality of this review and have included only those papers dealing with advances in the analysis of these materials. Other papers which the reader may find useful because they cover interesting applications are included in the tables. It follows last year's review1 and should be read in conjunction with other reviews in the series.2–5 Significant developments during this review period include the continued expansion of the use of LIBS in remote analysis, especially of explosives, metals and nuclear materials. The stand-off capability of the technique makes it very desirable in these areas. The use of chemometrics for removing substrate interferences is proving to be effective in making the technique more robustly quantitative and a number of papers developing the understanding of plasma physics to improve the technique of LIBS are reviewed. Multiple spectroscopic techniques are being developed to maximize the knowledge which can be derived from the analysis, especially of high value samples, for example the combination of LIBS and Raman measurements to gain molecular and atomic spectral information. Advances in the analysis of nanomaterials and single particles are reviewed and papers dealing with single particle analysis, field flow fractionation and related techniques coupled with ICP-MS are advancing the analytical chemistry in the field. These techniques are also increasingly being used in vivo and in biological areas. Depth profiling of semiconductor materials is an important area during this review period, especially for the determination of dopant elements. There are significant changes to the writing team this year. Mike Hinds has left the team and we are pleased to welcome Bridget Gibson and Ian Whiteside.

Atomic spectrometry update. Review of advances in the analysis of metals, chemicals and functional materials

Phosphorus loads are strongly associated with the severity of harmful algal blooms in Lake Erie, a Great Lake situated between the United States and Canada. Inorganic and total phosphorus measurements have historically been used to estimate nonpoint and point source contributions, from contributing watersheds with organic phosphorus often neglected. Here, we used ultrahigh resolution mass spectrometry to characterize the dissolved organic matter and specifically dissolved organic phosphorus composition of several nutrient pollutant source materials and aqueous samples in a Lake Erie tributary. We detected between 23 and 313 organic phosphorus formulas across our samples, with manure samples having greater abundance of phosphorus- and nitrogen containing compounds compared to other samples. Manures also were enriched in lipids and protein-like compounds. The greatest similarities were observed between the Sandusky River and wastewater treatment plant effluent (WWTP), or the Sandusky River and agricultural ...

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Discrete Organic Phosphorus Signatures are Evident in Pollutant Sources within a Lake Erie Tributary.

Simultaneous determination of phosphorus and boron in fertilizers was performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). Three different samples were analyzed, of which two were inorganic and one was of organic composition. Analysis of the samples was performed after heated acidic digestion to completely dissolve them, using two different acid mixtures. A solution of HCl + HNO3 was used to digest the inorganic fertilizers, and a solution of H2SO4 + HNO3 for the organic fertilizer. The spectral emission lines used were 213.617 nm and 214.917 nm for P and 249.772 nm, 249.677 nm and 208.957 nm for B. The detection and quantification limits for P were between 10–20 mg/kg and 40–80 mg/kg respectively, while for B they ranged between 10–30 mg/kg and 40–100 mg/kg respectively. The repeatability of the technique was found to be within the range 0.9–17.0% for P and 1.7–23.4% for B, expressed as relative standard deviation (RSD). The concentrations found by the proposed method are in good agreement with those reported on their package labels.

https://www.mdpi.com/2297-8739/5/3/36/pdf

Method Development of Phosphorus and Boron Determination in Fertilizers by ICP-AES

A systematic approach is proposed to evaluate microwave-assisted digestion in a single reaction chamber for the simultaneous determination of elements in the mineral fertilizer and raw material by inductively coupled plasma optical emission spectrometry. A reference material was digested using 12 acid mixtures containing nitric, hydrochloric, orthophosphoric, hydrofluoric or boric acid. Principal components analysis was applied for data treatment. Three digestion procedures based on diluted acids exhibited the most accurate results, with relative errors for reference values ranging from −15% to + 9%. Limits of quantification were in the range of 0.2 mg cadmium kg−1 up to 1000 mg aluminum kg−1.

Microwave-assisted digestion with a single reaction chamber for mineral fertilizer analysis by inductively coupled plasma optical emission spectrometry

In urban areas green roofs provide important environmental advantages in regard to biodiversity, storm water runoff, pollution mitigation and the reduction of the urban heat island effect. There is a paucity of literature comparing different types of green roof substrates and their contributions to ecosystem services or their negative effects. This study investigated if there was a difference between sedum and wildflower green roof substrate properties (soil organic matter (SOM), potassium (K) and phosphorus (P) concentrations and pH values) of 12 green roofs in the city of Brighton & Hove. One hundred substrate samples were collected (50 from sedum roof substrates and 50 from wildflower roof substrates) and substrate properties were investigated using standard protocols. Comparisons were made between substrate characteristics on both types of roof substrate with a series of multiple linear regressions. Sedum roofs displayed significantly higher values of SOM, P and pH. There were significant positive relationships between SOM and K concentrations, SOM and P concentrations, pH and K concentrations and pH and P concentrations on sedum roofs. This study concluded that sedum roof substrates are more favourable for plant water use efficiency and also contained a significantly higher percentage of SOM than wildflower roofs. However, higher concentrations of P in sedum roof substrates may have implications in regard to leachates.

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Up on the roof and down in the dirt: Differences in substrate properties (SOM, potassium, phosphorus and pH) and their relationships to each other between sedum and wildflower green roofs.

A two-part single-laboratory validation study was conducted for determination of the P and K content in commercial fertilizer materials by inductively coupled plasma-optical emission spectrometry (ICP-OES). While several methods exist for determination of P and K in fertilizer products, the main focus of this study was on ICP-OES determination, which offers several unique advantages. Fertilizer samples with consensus P and K values from the Magruder and Association of Fertilizer and Phosphate Chemists (AFPC) check sample programs were selected for this study. Validation materials ranging from 4.4 to 52.4% P205 (1.7 to 22.7% P) and 3 to 62% K20 (2.5 to 51.5% K) were utilized. Because all P and K compounds contained in fertilizer materials are not "available" for plants to use, this study was conducted in two parts. Part A focused on ammonium citrate-disodium EDTA as the extraction solvent, as it estimates the pool of fertilizer P and K that is considered available to plants. Part B focused on hydrochloric acid as the digestion solvent, as it estimates the total P and K content of the fertilizer product. Selectivity studies indicated that this method can have a high bias for fertilizer products containing sources of phosphite or organic P compared to gravimetric or colorimetric methods that measure just orthophosphate. Provided the analytical challenges outlined in this study are addressed, this method offers the potential for a quick, accurate, and safe alternative for determining the P and K content of commercial inorganic fertilizer materials.

Determination of phosphorus and potassium in commercial inorganic fertilizers by inductively coupled plasma-optical emission spectrometry: single-laboratory validation

Several methodologies are used throughout the world to determine phosphate concentration (measured as PO4 and expressed as % P2O5) in fertilizers. Concentrated phosphate materials, including diammonium phosphate (DAP) and monoammonium phosphate (MAP), are traded in large volumes (millions of metric tons) internationally. The International Fertilizer Association (IFA) identified a need to assess the methods currently being used to measure the phosphate content for suitability (scope), accuracy, and repeatability. Even small discrepancies in the expressed P2O5 content can have a major financial impact on buyers and sellers as contracts are settled and import regulations are imposed. The IFA's Technical Committee selected a working group to address issues dealing with harmonization of fertilizer sampling and analytical methodologies. The working group identified phosphate content in DAP and MAP fertilizers as a major concern for commerce. The working group initiated a method screening and comparison project to assess method performance and to determine which methods, if any, could be considered best practice methods and, therefore, be deemed acceptable for use by the industry. In order to systematically review the acceptability of methods for consideration, the task force developed an assessment protocol outlined in a white paper involving three steps: (1) compile all known relevant methods practiced in global fertilizer trade, (2) review and evaluate methods based upon specific evaluation criteria, and (3) compare the methods that most closely fit the evaluation criteria by multilaboratory analysis of unknown materials for accuracy and repeatability. Six methods were evaluated for analysis of total phosphate in concentrated phosphate products. From these methods, four were determined to be acceptable as best practice methods. The study members proposed three of the methods, while a fourth method was commonly used among the participating laboratories. This publication is a summary of the method comparison process and statistical evaluation of analysis of total phosphate content in concentrated phosphate fertilizers.

Sanford A Siegel

Papers

Determination of phosphorus and potassium in commercial inorganic fertilizers by inductively coupled plasma-optical emission spectrometry: single-laboratory validation

Evaluation of commonly used methods for the analysis of acid-soluble phosphate in internationally traded inorganic fertilizers.