Jeffrey R. Bacon

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.

Certified reference materials for the quality control of EDTA- and acetic acid-extractable contents of trace elements in sewage sludge amended soils (CRMs 483 and 484)

Abstract The ecotoxicity and mobility of trace elements in soils are often evaluated through analytical results resulting from operationally-defined determinations (single and sequential extractions), e.g. based on EDTA, acetic acid etc. extractions. The significance and comparability of these results is highly dependent on the procedures used (standardized protocols or standards adopted by international bodies) and their quality control relies on the availability of reference materials certified following these strictly applied procedures. Recognizing the need to harmonize some of the extraction schemes currently used for soil analysis, the Measurements and Testing Programme (formerly BCR) has organized a series of interlaboratory studies, the first aim of which was to evaluate EDTA- and acetic acid-extraction procedures and the second objective was to certify reference materials for their extractable trace element contents. Two sewage amended soils have been prepared for this purpose, originating respectively from Scotland and Catalonia. This paper describes the preparation, homogeneity and stability studies, and gives an overview of the certification campaign.

The changing nature of the 206Pb/207Pb isotopic ratio of lead in rainwater, atmospheric particulates, pine needles and leaded petrol in Scotland, 1982–1998

The inductively coupled plasma-mass spectrometry (ICP-MS)-determined 206Pb/207Pb ratio of 145 samples of rainwater collected at 25 locations around Scotland during December 1997 and January 1998 and at three longterm monitoring stations in the northeast, central belt and southeast of the country from November 1997 to December 1998 averaged 1.144+/-0.017 (1 s). This represents a significant increase from the mean value of 1.120+/-0.016 recorded for the long-term sites in 1989 1991, only partly attributable to a concomitant increase in the 206Pb/207Pb ratio of leaded petrol from 1.075+/-0.013 to 1.088+/-0.007. The rainwater 206Pb/207Pb data for the late 1990s also contrast markedly with the lower 206Pb/207Pb ratios found for pine needle and atmospheric particulate samples from Scotland (e.g. Glasgow: 1.085+/-0.012 in 1985-1986, 1.099+/-0.007 in 1991-1992), England and Western Europe in this study for the period 1982-1992 when emissions of lead to the atmosphere from petrol-engined vehicles in the UK were approximately 2-9 times higher. The observed change in the lead isotopic signature of rainwater predominantly reflects the impact of measures, such as the introduction and growing uptake of unleaded petrol, to reduce car exhaust emissions of lead to the atmosphere in the UK. Based on the rainwater data, source apportionment calculations suggest a general decline in the contribution of leaded petrol to atmospheric lead in Scotland from 53-61% in 1989-1991 to 32-45% in 1997-1998, with a corresponding decline in the urban environment from 84-86% to 48-58%.

Chemical and mineralogical forms of lead, zinc and cadmium in particle size fractions of some wastes, sediments and soils in Korea

Abstract Forms of Pb, Zn and Cd in the different size fractions ( 53 μm) of waste dumps, stream sediments and surrounding soils from a former Au mine in Korea, were investigated chemically by sequential extraction analysis and mineralogically by XRD and analytical SEM, so as to clarify the relationships between chemical and mineralogical forms. Total concentrations for the waste dumps and the stream sediments range from 655 to 2920 mg/kg for Pb, 565 to 1191 mg/kg for Zn, and 24.4 to 71.4 mg/kg for Cd, while those for the surrounding soils do not exceed the natural background levels. Direct observations on the heavy mineral fractions of the waste dumps and the stream sediments indicates that the primary sphalerite is still the main pool of the Zn and Cd, while a large part of the primary galena has been changed into a carbonate-bound form. This is in a good agreement with the partitioning of chemical forms in the coarse fractions, in which most of the Zn (75.3 to 79.4% for the waste dumps) and Cd (54.8 to 60.1% for the waste dumps) are associated with the oxidizable form, while most of the Pb (68.8 to 71.0% for the waste dumps) is in the acid (NaOAc)-extractable form. On the other hand, the partitioning of metal forms in the clay fraction is characterised by the highest proportion of the reducible form for all metals (56.6 to 73.8% for Pb, 60.2 to 68.4% for Zn, and 27.1 to 36.8% for Cd in the waste dumps), suggesting precipitation of easily to moderately reducible oxides and hydroxides from the other forms during weathering. With the increase of pH, the dramatic changes of the acid-extractable Pb, the oxidizable Zn and Cd in the coarse fractions, and the exchangeable form, especially for Cd in the clay fraction indicate that pH is the prime factor controlling the partitioning of heavy metals.

Polychlorinated biphenyls in UK and Norwegian soils: spatial and temporal trends

Contemporary soil samples from 46 sites across the UK and 12 sites in Norway have been analysed for a range of PCB congeners. Results show spatial differences, in terms of concentration and congener profile. The difference is partly caused by an increased proportion of the mid-molecular weight congeners in the samples from Norway. The soils from southern Norway and the UK contained similar amounts of PCBs per unit area: those from northern Norway contained lesser amounts. The possible influence of long-term air-soil exchange, latitudinal fractionation processes and differences in land management practices on the observed patterns is discussed. Archived soils (1951–1974) from the UK sites have also been analysed and the results show increasing concentrations of these compounds up to the late 1960s/early 1970s, after which there has been a substantial decline. This temporal trend is in accordance with that reported in previous studies. However, it is possible that some of the archived samples were contaminated in the process of air-drying. Due to this contamination artifact, it is not possible to ascertain whether the scale of the observed temporal differences truly reflect changes in the environment. The data are discussed in terms of possible spatial/temporal trends and the potential for air-soil exchange of these compounds.

COMPARISON OF SALT MARSH HUMIC ACID WITH HUMIC-LIKE SUBSTANCES FROM THE INDIGENOUS PLANT SPECIES SPARTINA ALTERNIFLORA (LOISEL)

Substances resembling humic acids were extracted from fresh plant material (Spartina alterniflora) and from dead plant debris. Their elemental composition, spectral characteristics in the UV, visible and IR regions, and electron spin resonance were compared with those of humic acid from mud in which the plants were growing. The results show the plant humic substances to consist of a higher portion of aliphatic compounds in their complex structures than that from mud. However, the overall similarities between the extracted material from the different sources indicate that S. alterniflora makes a direct contribution to the humic substances in the salt marsh ecosystems.

Persistence and fate of polychlorinated biphenyls (PCBs) in sewage sludge-amended agricultural soils.

Four metal enriched sewage sludges containing different concentrations of polychlorinated biphenyls (PCBs) were applied to two field soils in the UK in 1968. Samples of the sludges, sludge-amended soils and soils from untreated control plots were stored and analysed retrospectively. Sludge concentrations ranged from 1 to 7 mg SigmaPCB kg(-1). The pattern of PCBs was similar in three of the four sludges, with congeners 14, 18, 28 and 52 present at the highest concentrations. The fourth sludge contained higher amounts of congeners 149, 153, 138 and 180. SigmaPCB concentrations in control plot soil have declined over the last 20 years, indicating a reduction in atmospheric deposition inputs of PCBs to the soil. SigmaPCB concentrations also declined on the sludge-amended plots, reaching control plot concentrations (30-60 microg SigmaPCB kg(-1)) in the late-1980s. Half-lives ranged from < 1 to 8.5 years for congeners 18, 28 and SigmaPCB. Biodegradation and/or the formation of reversibly sorbed soil PCB residues could not account for the losses observed. Volatilisation is implicated as the most important loss process on both the control and sludge-amended plots. Using the fugacity approach, congener concentrations in soils at Luddington were predicted still to have not reached equilibrium with the air. Further losses to the atmosphere are likely.

Multiple profiling of soil microbial communities identifies potential genetic markers of metal‐enriched sewage sludge

The long-term impacts of Cu- and Zn-rich sewage sludge additions on the structure of the microbial community in a field under pasture were investigated using a combination of multiplex-terminal restriction fragment length polymorphism (M-TRFLP) and T-RFLP profiling approaches. Changes in the community structure of bacteria, fungi, archaea and actinobacteria were observed in soils that had previously received Cu- (50-200 mg kg(-1) soil) and Zn- (150-450 mg kg(-1) soil) rich sewage sludge additions. Changes in the structure of all microbial groups measured were observed at Cu and Zn rates below the current EU guidelines (135 mg kg(-1) Cu and 300 mg kg(-1) Zn). The response of the fungal community, and to a lesser extent the bacterial and archaeal community, to Cu was dose dependent. The fungal community also showed a dose-dependent response to Zn, which was not observed in the other microbial groups assessed. Redundancy analysis demonstrated that individual terminal restriction fragments responded to both Cu and Zn and these may have potential as genetic markers of long-term metal effects in soil.

Determination of the extent of anthropogenic Pb migration through fractured sandstone using Pb isotope tracing

Abstract The extent of vertical migration of anthropogenic Pb beneath a medieval smelting site in Derbyshire, U.K. has been estimated using the determination of total Pb concentrations and 206 Pb/ 207 Pb isotope ratio from samples taken down 6 m of drill core. Preliminary studies of total Pb concentrations established that the surface slag derived from the smelting contained up to 16% Pb and that the normal background levels in uncontaminated sandstone were 10±2 ppm. Sample analyses beneath the site revealed elevated Pb concentrations in fracture infill clays (270 ppm Pb) and sandstone (76–83 ppm Pb). Both are well above the background Pb concentration. Lead isotope analysis of the slag wastes, the underlying contaminated sandstone and fracture infill has shown that all 3 contain very similar isotope ratios for 206 Pb/ 207 Pb (1.1802–1.1820). However, matched control sandstone samples show that the background 206 Pb/ 207 Pb isotope ratio (1.1670 ± 0.003) is distinctly different. This would indicate that both the sandstone and fracture infill underlying the historical smelting site contain a substantial proportion of Pb that has been derived from the overlying contamination. The application of total Pb concentrations along the core and isotope analysis suggest that anthropogenically derived Pb from the smelting site (that was operated between 665 and 445 a BP) has migrated to a depth of 4.50 m. Assuming a uniform migration rate and a mean time of migration of 555 a, then the mean migration rate is estimated to be 8 ± 2 mm/a. The proportion of natural versus anthropogenic Pb in the samples has been estimated from small variations in the 206 Pb/ 207 Pb isotope ratio. If the slag is considered to contain 100% anthropogenic Pb and the uncontaminated sandstone considered to contain 100% natural Pb, the linear interpolation can be applied between the 2 end members of the isotope ratio. The use of this approach to the 206 Pb/ 207 Pb ratio measurements has shown that 88% of the Pb in the contaminated sandstone (i.e. 69 ppm from a mean total Pb concentration of 78.5 ppm) has been derived from the anthropogenic Pb at the surface. For the fracture infill sample taken at a depth of 4.50 m, and with a total Pb concentration of 270 ppm, the % of Pb that has been derived from the slag wastes is approximately 98% (equivalent to 265 ppm Pb). The remaining Pb in both these samples (9.4 and 5 ppm, respectively) is deduced to have originated from the natural background concentration of Pb in the sandstone. The closeness of these estimates to the measured background concentration, suggests that a simple two-source model of Pb contamination is valid for this site.

Characterization of environmental water samples using strontium and lead stable isotope compositions

A simple procedure using both cation and anion exchange chromatography has been applied in the study of lead and strontium isotope composition in rain and stream water samples from remote catchments in Scotland. Whereas the soil released strontium to stream waters, lead was removed from rain water and the concentrations in stream waters were very low. Highly precise analysis by thermal ionisation mass spectrometry proved necessary in the determination of strontium isotope composition. The 87Sr/86Sr ratio in rain water was close to that of marine strontium but the ratios in stream waters were constant and highly characteristic for the stream. In the case of the stream at the Sourhope site, the ratio (0.70798 ± 0.00005) was less than that in rain water and probably resulted from the weathering of one specific mineral. The results suggested that the 87Sr/86Sr ratios could be used as a stable isotope tracer of waters and to provide information on the weathering processes. Two major anthropogenic components of lead were identified in water samples. One had its origin in petrol additives whereas the other was probably of industrial origin. The low 206Pb/207Pb ratios observed in stream waters confirmed the lead as being of anthropogenic origin and the data suggested that there was a movement, albeit very small, of lead from the soil to waters.