On- and off-line analysis by ICP-MS to measure the bioaccessible concentration of elements in PM10 using dynamic versions of the simplified bioaccessibility extraction test.

Two dynamic versions of the simplified bioaccessibility extraction test (SBET) were developed-an off-line procedure and an on-line procedure coupled directly to ICP-MS. Batch, on-line, and off-line procedures were applied to simulated PM10 samples prepared by loading NIST SRM 2711A Montana II Soil and BGS RM 102 Ironstone Soil onto 45-mm TX40 filters widely used in air quality monitoring. Three real PM10 samples were also extracted. A polycarbonate filter holder was used as an extraction unit for the dynamic procedures. Arsenic, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined in the extracts using an Agilent 7700 × ICP-MS instrument. The residual simulated PM10 samples following application of the SBET were subjected to microwave-assisted aqua regia digestion and a mass balance calculation performed with respect to digestion of a separate test portion of the SRM. Leachates were collected as subfractions for the off-line analysis or continuously introduced to the nebuliser of the ICP-MS for the on-line analysis. The mass balance was generally acceptable for all versions of the SBET. Recoveries obtained with the dynamic methods were closer to pseudototal values than those obtained in batch mode. Off-line analysis performed better than on-line analysis, except for Pb. Recoveries of bioaccessible Pb relative to the certified value in NIST SRM 2711A Montana II Soil (1110 ± 49 mg kg-1) were 99, 106, and 105% for the batch, off-line, and on-line methods, respectively. The study demonstrates that dynamic SBET can be used to measure bioaccessibility of potentially toxic elements in PM10 samples.

A circular economy approach to drinking water treatment residue management in a catchment impacted by historic metal mines.

Drinking water treatment residues (DWTR) from mining areas which remove and contain potentially toxic elements (PTE) could still potentially be used as a soil amendment to restore contaminated sites in the same catchment, thus eliminating waste and reducing the chemical and physical mobility of the pollutants. To assess this restorative and regenerative approach to DWTR management, field and pot trials were established with soils from a historic Pb-Zn mine site in the North East of England, amended with either local DWTR or the nearest available municipal green waste compost (GWC). Soils from the mine site were found to have very low levels of nutrients and very high levels of PTE (Pb and Zn > 13, 000 mg/kg). The perennial grass species Phalaris arundinacea, known for many ecosystem service benefits including soil stabilization, was used throughout this study. The application of the BCR sequential extraction to soils amended with the DWTR in the pot trials found a significant decrease in the bioavailability of Pb and Cu (p < 0.05) after plant growth when compared with an unamended control. The field trial involved 648 pre-grown grass plants planted-out into mine soils amended with either DWTR, GWC or a mixture (MIX) of the two, all at rates of 25-30% w/w. Both amendments and the MIX had significant positive effects on biomass production compared to the unamended control in the following order GWC > MIX > DWTR (p < 0.05). Results of the elemental analysis of biomass from the field trial were generally ambiguous and did not reflect the decreased bioavailability noted in the pot trials using the BCR procedure. Pot trials, however, showed increases in plant growth and decreases in concentrations of Cr, Cu, Pb and Zn in above ground biomass following the application of both amendments. Further work should involve the testing of a mixture of DWTR and other soil amendments to enhance plant growth. The success of these trials should provide confidence for those working in drinking water treatment and catchment management to reuse the waste residues in a circular economy and a sustainable way that could improve water quality over time.

Mobility, spatial variation and human health risk assessment of mercury in soil from an informal e-waste recycling site, Lagos, Nigeria.

Spatial variations and mobility of mercury (Hg) and Hg associations with other potentially toxic elements (PTEs) were studied in soil samples from Alaba, the largest e-waste recycling site in Nigeria and West Africa. Total Hg concentration was determined in surface soil samples from various locations using cold vapour atomic absorption spectrometry (CVAAS) following microwave-assisted acid extraction, while sequential extraction was used to determine operationally defined mobility. The concentrations of the PTEs arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) metals were determined using inductively coupled plasma mass spectrometry (ICP-MS) following microwave-assisted digestion with aqua regia. Total Hg concentration ranged from < 0.07 to 624 mg/kg and was largely dependent on the nature and intensity of e-waste recycling activities carried out. Mobile forms of Hg, which may be HgO (a known component of some forms of e-waste), accounted for between 3.2 and 23% of the total Hg concentration, and were observed to decrease with increasing organic matter (OM). Non-mobile forms accounted for >74% of the total Hg content. In the main recycling area, soil concentrations of Cd, Cd, Cu, Hg, Mn, Ni, Pb and Zn were above soil guideline values (Environment Agency in Science Report, 2009; Kamunda et al., 2016). Strong associations were observed between Hg and other PTEs (except for Fe and Zn) with the correlational coefficient ranging from 0.731 with Cr to 0.990 with As in April, but these correlations decreased in June except for Fe. Hazard quotient values > 1 at two locations suggest that Hg may pose health threats to people working at the e-waste recycling site. It is therefore recommended that workers should be investigated for symptoms of Hg exposure.

Assessing Mercury Mobility in Sediment of the Union Canal, Scotland, UK by Sequential Extraction and Thermal Desorption.

The mobility of mercury (Hg) was assessed in sediment from the Union Canal, Scotland, UK. Samples collected from the vicinity of a former munitions factory that manufactured mercury fulminate detonators were subjected to sequential extraction followed by cold vapor atomic absorption spectrometry (CVAAS) and direct analysis using thermal desorption (TD). The sequential extraction indicated that > 75% of mercury (up to 429 mg kg-1) was in mobile forms, with < 12% semimobile and < 23% nonmobile species. In the TD method, > 67% of the total Hg content was desorbed in the temperature range 100-250 °C consistent with species weakly attached to the mineral matrix [tentatively identified as an iron (oxy)hydroxide-associated species]. This predominance of mobile mercury species may arise from a lack of association between Hg and either organic matter or sulfur in the sediments. Further investigation of Hg mobilization, transport, and assimilation/biomagnification is required both to determine whether there is a need for remediation of the sediment and to improve understanding of the biogeochemical cycling of Hg in shallow, oxic, freshwater systems.

Kinetic field dissipation and fate of endosulfan after application on Theobroma cacao farm in tropical Southwestern Nigeria.

Endosulfan, 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano,2,4,3-benzodioxathiepin-3-oxide, is still a pesticide of choice for most cocoa farmers in Southwestern Nigeria, in spite of its persistence, bioaccumulative, toxicological properties, and restriction. A single treatment of 1.4 kg ai/ha (0.5% ai) of technical grade endosulfan (Thiodan, 35EC) was applied to 0.0227 ha of cultivated Theobroma cacao L. (Cocoa) farm at the Cocoa Research Institute of Nigeria (CRIN). Levels of parent endosulfan (α-, ß-endosulfan) and major metabolite (endosulfan sulfate) were determined in vegetation and surrounding matrices at days 0, 7, 14, 21, 28, 42, and 60 using GC-MS. Their kinetic variables were determined. Order of ∑endosulfan distribution at day 0 was dry foliage > fresh foliage > bark > pods > soil (0-15 cm). No residual endosulfan was found in cocoa seeds and subsurface soil (15-30 cm). Low residual levels in pods on day 0 may be due to endogenous enzymatic breakdown, with α-isomer more susceptible and α/ß-endosulfan ratio being 0.90. Fell dry foliage as mulch was predominantly the receiving matrix for non-target endosulfan sprayed. Volatilization was key in endosulfan dissipation between days 0 and 7 from foliage surfaces (> 60% loss), while dissipation trend was bi-phasic and tri-phasic for vegetation and soil, respectively. ∑endosulfan loss at terminal day ranged between 40.60% (topsoil) and 99.47% (fresh foliage). Iteratively computed half-lives (DT'50) ranged from 6.48 to 30.13 days for ∑endosulfan in vegetation. Endosulfan was moderately persistent in pods-a potential source for cross contamination of seeds during harvest. Iteratively determined DT'50 and initial-final day DT50 are highly correlated (R = 0.9525; n = 28) and no significant difference (P = 0.05) for both methods.

Optimization and application of a low cost, colorimetric screening method for mercury in marine sediment.

A rapid, inexpensive, colorimetric screening method for mercury (Hg) has been optimized to provide a semi-quantitative measurement of Hg concentration in marine sediment within the range 0.038 to 1.5 mg kg-1 encompassing the interim sediment quality guideline (ISQG) value of 0.13 mg kg-1 (CCME 1999) and the probable effects level (PEL) of 0.7 mg kg-1 for Hg in marine sediment (CCME 1999). Neither salinity (up to 41 practical salinity units (psu)) nor sediment organic matter (ΟΜ) content (up to 10%) affected the performance of the method. Accurate results were obtained for spike recovery experiments and analysis of certified reference material (CRM) BCR 580 Estuarine Sediment. The method was applied to sediment samples from Elefsina Bay, Greece. Screening results indicated Hg contamination in the bay, with concentrations exceeding the PEL value. Findings were confirmed by quantitative analysis of the samples by cold vapor atomic absorption spectrometry (CV-AAS), where results in the range 1.4-2.96 mg kg-1 were determined.

A novel two-step sequential bioaccessibility test for potentially toxic elements in inhaled particulate matter transported into the gastrointestinal tract by mucociliary clearance.

A novel two-step sequential extraction has been developed to assess the bioaccessibility of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in airborne particulate matter following inhalation and transport into the human gastrointestinal tract by mucociliary clearance. A new artificial mucus fluid (AMF) was used to determine the bioaccessible potentially toxic element (PTE) fraction in the upper airways, in sequence with the simplified bioaccessibility extraction test (SBET) or the stomach phase of the unified bioaccessibility method (gastric fluid only) (UBMG). Filter dynamic measurement system TX40 filters smeared with soil reference material (BGS RM 102) were used as test samples. Analysis was performed by ICP-MS. Comparison between results obtained for soil alone and when the soil was supported on TX40 filters indicated that the presence of the substrate did not affect the extraction efficiency, although a large Zn blank was detected. The sequential AMF→SBET extraction liberated similar amounts of Fe, Mn, Ni and Zn to the SBET alone; but significantly less Cd; and significantly more As, Cr, Cu and Pb. The sequential AMF→UBMG extraction liberated similar amounts of Cd, Cr, Mn and Zn to the UBMG alone, but significantly less As, Fe and Ni; and significantly more Cu and Pb. Enhanced extractability was due to the greater quantities of exchangeable ions and complexing agents present. Adoption of a two-step sequential extraction (AMF followed by either the SBET or the UBMG) is recommended because it is more representative of biological conditions and avoids overestimation or underestimation of bioaccessible PTE concentrations. Graphical Abstract Simulated PM10 sample: BGS RM 102 ironstone soil on TX40 filter.

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon, Nigeria, West Africa.

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.

Potentially Toxic Elements in Urban Soils from Public-Access Areas in the Rapidly Growing Megacity of Lagos, Nigeria.

Rapid urbanization can lead to significant environmental contamination with potentially toxic elements (PTEs). This is of concern because PTEs are accumulative, persistent, and can have detrimental effects on human health. Urban soil samples were obtained from parks, ornamental gardens, roadsides, railway terminals and locations close to industrial estates and dumpsites within the Lagos metropolis. Chromium, Cu, Fe, Mn, Ni, Pb and Zn concentrations were determined using inductively coupled plasma mass spectrometry following sample digestion with aqua regia and application of the BCR sequential extraction procedure. A wide range of analyte concentrations was found­Cr, 19−1830 mg/kg; Cu, 8−11,700 mg/kg; Fe, 7460−166,000 mg/kg; Mn, 135−6100 mg/kg; Ni, 4−1050 mg/kg; Pb, 10−4340 mg/kg; and Zn, 61−5620 mg/kg­with high levels in areas close to industrial plants and dumpsites. The proportions of analytes released in the first three steps of the sequential extraction were Fe (16%) < Cr (30%) < Ni (46%) < Mn (63%) < Cu (78%) < Zn (80%) < Pb (84%), indicating that there is considerable scope for PTE (re)mobilization. Human health risk assessment indicated non-carcinogenic risk for children and carcinogenic risk for both children and adults. Further monitoring of PTE in the Lagos urban environment is therefore recommended.

Comparison of two non-specific flow-through sequential extraction approaches to identify the physico-chemical partitioning of potentially harmful elements in a certified reference material.

Two non-specific sequential extraction methods utilising chemometric data processing (chemometric identification of substrates and element distribution, CISED) have been developed and used to determine the physico-chemical partitioning of potentially harmful elements (PHE) in certified reference material BCR CRM 701 (lake sediment). A miniaturized centrifugation method in which the sample was extracted on a filter insert in a polypropylene centrifuging tube, and a quasi-flow through method in which the sample was supported on a TX40 filter in a 47 mm in-line polycarbonate filter holder, gave similar results. The CISED data processing identified nine components. Seven of these were of geochemical origin - two carbonate components, an Al/Fe oxide/hydroxide component, three Fe-dominated components and one Si-dominated component - while the others represented the TX40 filter blank. The overall extraction capabilities of the methods were similar to that of the well-established BCR sequential extraction (Σsteps 1-3). However, whilst the BCR extraction is operationally defined, the CISED provides information on associations between PHE and the geochemical components identified. The flow through CISED procedure has potential applications in investigating the chemical speciation of PHE associated with urban airborne particular matter.

Use of a physiologically based extraction test to estimate the human bioaccessibility of potentially toxic elements in urban soils from the city of Glasgow, UK.

A simple, two-stage, physiologically based extraction has been applied to assess the human bioaccessibility of potentially toxic elements (PTE) in 20 urban soils from a major UK city. Chromium and iron bioaccessibilities were found to be markedly higher in the intestinal phase, whilst lead and zinc bioaccessibilities were higher in the stomach. Copper and manganese bioaccessibilities were generally similar under both extraction conditions. Principal component analysis was used to study relationships amongst bioaccessible element concentrations and land use. Distinctions could be observed between the distributions of the urban metals-copper, lead and zinc-and metals predominantly of geogenic origin, such as iron. There was no clear delineation between roadside soils and soils obtained from public parks. Bioaccessible analyte concentrations were found to be correlated with pseudototal (aqua regia soluble) analyte concentrations for all elements except iron. Results of the BCR sequential extraction did not, in general, provide a good indication of human bioaccessibility. Comparison of bioaccessible PTE concentrations with toxicological data indicated that lead is the element of greatest concern in these soils but that levels are unlikely to pose a health risk to children with average soil intake.

GC-MS fragmentation patterns of sprayed endosulfan and its sulphate metabolite in samples of Theobroma cacao L from a field kinetic study.

Most environmental analytical methods for the determination of organochlorine pesticides (OCPs) are multi-residual with other organic compounds co-extracted and co-eluted. This has been observed in GC spectra using classical detectors like electron-capture detector (ECD) even after appropriate clean-up. This limitation could be resolved by using GC-MS methods which are more specific and selective. Thus, a commercial-grade endosulfan treated Theobroma cacao plantation was sampled. Representative samples comprising leaves, stem bark and pulp were obtained between 0.5 h and 60 days after treatment. Samples were analyzed for residual parent endosulfan (α- and ß-isomers) as well as the metabolite endosulfan sulphate using an ion trap GC-MS. The retention times and chromatogram peaks obtained for various endosulfan were identified and compared with reference standards, and confirmed with National Institute of Standards and Technology library. Results showed that the molecular ion at m/z 407 was exhibited by α- and ß-endosulfan, representing the parent molecular ion M+• ([C9H6Cl6SO3]+•). The α-isomer was more thermally stable, hence exhibited more relative abundance. Other predominant peaks were 339, 307, 277, 265, 243, 241, 207, 195, 160, 159, 99 and 75 m/z. The peak at m/z 159 was the base molecular ion. For endosulfan sulphate, the peak at m/z 422 corresponded to parent molecular ion (M+•), while m/z 424 was due to isotopic pattern characteristic of the chlorine atom. The peaks at 387, 357, 289, 272, 229, 206, 170, and 120 m/z were characteristic for the sulphate metabolite. The m/z peak at 272 was the base molecular ion, while m/z 143 may be due to metabolite diol and lactone. These results showed that the various endosulfan species can be identified and confirmed simultaneously using a GC-MS.

Effects of sample pretreatment and particle size on the determination of nitrogen in soil by portable LIBS and potential use on robotic-borne remote Martian and agricultural soil analysis systems.

Field determination of nitrogen in soil is of interest for both terrestrial and Martian applications. Improved management of soil nitrogen levels on Earth could benefit global food production, whilst the determination of soil nitrogen on Mars is required to assess the planet's future habitability. In this study, a mobile laser induced breakdown spectroscopy (LIBS) system with a 1064 nm Nd:YAG laser delivering 25 mJ per pulse was used to assess the effects of sample pretreatment on the measurement of nitrogen in soil. Although pelletisation was preferred, simply milling the sample to <100 mm particle size - which may be more feasible on a remote rover-based analytical platform - improved the spectra obtained. Ablation craters formed in targets prepared from different particle size fractions of the same commercially-available topsoil showed a clear trend in morphology, with smaller particles yielding more uniform craters with fewer fractures. The LIBS emission intensity at 746.83 nm followed a similar trend to results obtained for total nitrogen content in the soil particle size fractions by microanalysis (Perkin Elmer CHN Elemental Analyser) and was well-correlated (R 2 = 0.94) with soil nitrate determined by ion chromatography (Dionex DX-100). Although correlations were less good when analysing field soil samples collected from central Scotland (R 2 = 0.82 for comparison between LIBS and microanalysis) the study nevertheless demonstrates the potential of portable LIBS for measurement of soil nitrogen content.

The long-term environmental behaviour of strontium and barium released from former mine workings in the granites of the Sunart region of Scotland, UK.

The concentrations of strontium and barium have been measured in water, sediment and the shells of mussels (Mytilus edulis) from a river system in the Sunart region of Scotland, UK. The aim was to establish the fate and mobility of these elements, which are slowly being released from old mine workings on the Strontian granites. Enhanced strontium (1500-2000 microg l(-1) and 250-290 microg l(-1)) and barium concentrations (316 microg l(-1) and 83 microg l(-1)) were found in the waters originating from the two mine drains studied. Both element were also found at significant levels in the river sediments taken from the vicinity of each drainage site (Sr: 225 microg g(-1) and 120-125 microg g(-1); Ba: 1380 microg g(-1) and 126-170 microg g(-1)). The data suggests that the sediments are acting as a reservoir for these group II cations from where they become distributed throughout the river system. Strontium is found to be incorporated into the shells (3.16-3.46 microg g(-1)) and pearls (3.57 microg g(-1)) of the blue mussel, located at the estuarine margin some 10 km downstream, at values close to the maximum expected (3.3% by weight of the calcium content). The study presents a view of the fate of barium and strontium in a river system over a prolonged period of time. As such it provides valuable information for studies that seek to model the impact of the accidental release of barium and strontium (including the important radionuclide 90Sr) into the environment.

Large pore diameter MCM-41 and its application for lead removal from aqueous media.

A room temperature method to create large pore size and pore volume ordered mesoporous silica (MCM-41) is demonstrated. Template removal was achieved with a microwave digestion procedure using a solution of nitric acid and hydrogen peroxide. The silica product exhibited an ordered hexagonal mesostructure, large pore volume (up to 0.99 cm(3)/g), and large pore size (up to 6.74 nm) indicating its potential as a high capacity adsorbent. Surface modification, to enhance the ability of the material to extract potentially toxic metals (PTMs) from water was performed using different amino- and mercapto-functional groups. This paper reports on the extraction of lead ions from aqueous solution to demonstrate the material's significant improvement in adsorption capacity (up to 1000 µmol g(-1) for lead). Moreover, methods have been developed to regenerate the sorbent allowing 100% recovery of Pb and reuse of the sorbent material in subsequent extractions. The performance of the material was also demonstrated for environmental samples containing relatively high concentrations (ppmv) of mixed metal ions reducing them to lower values (<100 ppbv) indicating that the sorbent may have applicability for environmental remediation of polluted water.

Extractability and mobility of mercury from agricultural soils surrounding industrial and mining contaminated areas.

This study focussed on a comparison of the extractability of mercury in soils with two different contamination sources (a chlor-alkali plant and mining activities) and on the evaluation of the influence of specific soil properties on the behaviour of the contaminant. The method applied here did not target the identification of individual species, but instead provided information concerning the mobility of mercury species in soil. Mercury fractions were classified as mobile, semi-mobile and non-mobile. The fractionation study revealed that in all samples mercury was mainly present in the semi-mobile phase (between 63% and 97%). The highest mercury mobility (2.7 mg kg(-1)) was found in soils from the industrial area. Mining soils exhibited higher percentage of non-mobile mercury, up to 35%, due to their elevated sulfur content. Results of factor analysis indicate that the presence of mercury in the mobile phase could be related to manganese and aluminium soil contents. A positive relation between mercury in the semi-mobile fraction and the aluminium content was also observed. By contrary, organic matter and sulfur contents contributed to mercury retention in the soil matrix reducing the mobility of the metal. Despite known limitations of sequential extraction procedures, the methodology applied in this study for the fractionation of mercury in contaminated soil samples provided relevant information on mercury's relative mobility.

Is there a future for sequential chemical extraction?

Since their introduction in the late 1970s, sequential extraction procedures have experienced a rapid increase in use. They are now applied for a large number of potentially toxic elements in a wide range of sample types. This review uses evidence from the literature to consider the usefulness and limitations of sequential extraction and thereby to assess its future role in environmental chemical analysis. It is not the intention to provide a comprehensive survey of all applications of sequential extractions or to consider the merits and disadvantages of individual schemes. These aspects have been covered adequately in other, recent reviews. This review focuses in particular on various key issues surrounding sequential extractions such as nomenclature, methodologies, presentation of data and interpretation of data, and discusses typical applications from the recent literature for which sequential extraction can provide useful and meaningful information. Also covered are emerging developments such as accelerated procedures using ultrasound- or microwave energy-assisted extractions, dynamic extractions, the use of chemometrics, the combination of sequential extraction with isotope analysis, and the extension of the approach to non-traditional analytes such as arsenic, mercury, selenium and radionuclides.