Thomas C. Hutchinson

Analysis of tree rings using inductively coupled plasma mass spectrometry to record fluctuations in a metal pollution episode.

Analysis of Acer pseudoplatanus L. (sycamore) tree rings using ICP-MS was used to assess the impact of metal deposition on trees growing in the vicinity of a metal refinery at Prescot, north-west England compared to a reference site at Croxteth 6 km distant receiving minimal deposition. No difference in tree growth between sites was recorded. Large reductions in Cu and Cd deposition since the late 1970s was accompanied by a steep decline in Cd concentrations in the outer rings in trees close to the refinery. A similar reduction in Cu concentrations was less apparent due to a tendency for Cu to increase in the outer rings. Zinc and Ni were higher in xylem at Prescot compared to Croxteth. There was no trend in Zn concentrations at either site although Ni concentrations increased in trees close to the refinery after 1982. Manganese concentrations in xylem were much higher at Prescot; Mn levels declined until the late 1970s and then increased slightly in later years interspersed by large concentration peaks within individual years during the 1980s. There was little change in Mn concentrations in trees at Croxteth during this period. Calcium, Mg and Sr concentrations remained steady or declined slightly in rings formed since 1965 in trees at Croxteth. Concentrations of Ca, Mg and Sr were higher in rings formed prior to the mid 1970s in trees at Prescot, but declined steadily after this period, although peaks in concentrations of each element were recorded in individual years during the 1980s. Phosphorous concentrations in rings increased towards the cambium at Croxteth, although P levels decreased in rings formed after 1982 at Prescot. No difference in K concentrations between sites was recorded. Lead concentrations in xylem at both sites declined steadily in rings formed after 1970, although concentrations were higher at the reference site. Analysis of individual sycamore tree rings appears to record short-term changes in pollution episodes, with little lateral movement of elements occurring. It is suggested that changes in element concentrations in trees close to the refinery are a result of reduced metal deposition combined with increased soil acidity due to reduced buffering capacity of metal ions in rainfall.

Historical changes in lead concentrations in tree-rings of sycamore, oak and Scots pine in north-west England.

Lead concentrations in tree rings of sycamore (Acer pseudoplatanus L.), oak (Quercus robur L.) and Scots pine (Pinus sylvestris L.) sampled at a parkland in north-west England were measured in wood formed since the mid-1800s. Concentrations of Pb in Scots pine and oak peaked in wood formed between 1900 and 1940, most likely because of Pb accumulation in heartwood, indicating that oak and Scots pine are unsuitable for monitoring temporal changes in Pb deposition at the study site. In contrast, Pb concentrations in sycamore, a species that has similar heartwood and sapwood chemistry, were relatively constant in wood formed between the mid-1800s and 1950. Lead concentrations decreased steadily in sycamore tree rings formed after the 1950s, and decreased more abruptly in wood formed after 1985. This sharp decrease in wood Pb cannot be due to decreases in soil Pb concentration. Stable Pb isotope analysis was used to further investigate Pb patterns in sycamore wood. Excess 206Pb/207Pb ratios in tree-rings of sycamore were relatively constant, approximately 1.17, in wood formed prior to the 1930s, but decreased steadily thereafter reaching a minimum value of approximately 1.16 in wood formed between 1975 and 1985 after which time 206Pb/207Pb ratios increased. This pattern is consistent with changes in Pb isotope ratios measured in peat, sediment and aerosol samples in the UK. However, the magnitude of the decrease in 206Pb/207Pb (largely due to gasoline Pb) is considerably lower than in other studies and our estimates indicate that less than 20% of the total Pb in sycamore wood measured since the mid-1800s is derived from gasoline emissions. A more likely explanation for the pattern of Pb observed in sycamore tree rings is that soil Pb accumulates within rings of the diffuse porous wood over a number of years. Such uptake patterns would result in lower Pb concentrations in the outer (more recently formed) tree rings, which coincide with recent reductions in Pb deposition in the UK. Overall, this study indicates that tree ring chemistry is unsuitable for monitoring historical changes in Pb deposition at the study site.

Change in the dendrochemistry of sacred fir close to Mexico City over the past 100 years

The chemistry of the tree-rings of sacred fir (Abies religiosa) growing in the high elevation forest park, Desierto de los Leones, close to Mexico City was measured in 5 year increments dating back to 1897. Surface soil beneath sampled trees had elevated concentrations of trace metals, especially Pb, Cd and Zn, compared with a reference site at San Pablo 45 km upwind of Mexico City. High metal concentrations were associated with low soil pH. Lead and Cd increased in tree-rings formed since the 1960s, reflecting the increase in urbanization and vehicle numbers in Mexico City. Small increases in Cu and Ni during this period appear to be a natural occurrence, as similar changes were found at San Pablo. Peaks in Cd and most obviously Pb, were found in rings formed in the period 1920–1940 corresponding to the heartwood–sapwood boundary, but were most apparent in trees growing in contaminated soils with low pH. It is suggested that Pb and Cd taken up by roots of sacred fir accumulate in the heartwood, whereas Pb and Cd entering through bark are transported radially to a much lesser extent and more accurately record changes in trace metal deposition.

Uptake of 207Pb and 111Cd through bark of mature sugar maple, white ash and white pine: a field experiment.

A field study was undertaken to determine whether 207Pb and 111Cd, applied to the exterior bark of sugar maple (Acer saccharum Marsh.), white ash (Fraxinus americana L.) and white pine (Pinus strobus L.), could enter xylem tissue. Stable isotope tracers (3 microg Pb ml(-1); 2 microg Cd ml(-1)) were applied separately to bark in simulated rainfall, acidified to pH 4.5, in multiple doses over a 4 month (July-October) period. Tree cores were extracted from the region of application in the following March, and Pb and Cd isotopes were measured in bark and the outer tree rings using inductively coupled plasma mass spectrometry. The majority of the applied stable isotope tracer recovered (over 94%) was present in bark tissue, although a small amount of each metal tracer entered the outer (1-3) tree rings in all trees. Despite high concentrations of excess 207Pb in bark (up to 50 microg g(-1)), the maximum concentration of excess 207Pb measured in tree rings was only around 50 ng g(-1), which represents less than 30% of the background Pb concentration in wood at the study site. High excess 111Cd concentrations in bark (up to 35 microg g(-1)) also resulted in small increases in 111Cd in wood (up to 50 ng g(-1)), but due to lower background Cd concentrations in wood, such increases more than doubled the amount of Cd in wood compared with background levels. However, at sites where such high bark Cd concentrations are found, uptake from Cd-contaminated soil would probably be much greater than found at our study site. It appears that Cd and Pb applied to bark can enter woody tissue, but that this route of uptake is likely to be a minor contributor to the metal burden in wood.

Changes in tree ring chemistry in sugar maple (Acer saccharum) along an urban-rural gradient in southern Ontario

Changes in xylem chemistry in sugar maple (Acer saccharum Marsh.), sampled from four woodland sites along an urban–rural gradient were examined. Two sites were located 4 km apart within metropolitan Toronto, a third was adjacent to a major highway 24 km north-east of Toronto and a rural site was chosen 150 km to the north-east of Toronto along the prevailing wind direction. Concentrations of Pb and Cu in surface soil were elevated at the two city centre sites and the highway site compared to the rural woodland, but only the city site (which was located close to major roads) and the highway site had elevated Zn, Cr and V. Pb concentrations in tree rings were highest at the two city centre sites, but a steady decline from around 1 mg kg−1 dry wt in wood formed in the early 1920s to present levels of 0.5 mg kg−1 dry wt was recorded. In contrast, Pb levels were low at the highway site in wood formed prior to the 1940s, but increased dramatically to peak around 1.5 mg kg−1 dry wt in the 1950s and then declined during the 1960s to levels comparable to the city sites. Pb concentrations at the rural woodland were consistently less than 0.2 mg kg−1 dry wt. Concentrations of all other trace elements in xylem were approaching detection limits by inductively coupled plasma mass spectrometry (ICP–MS). No difference in Ca, Fe, K, Mg, Mn, P or Sr concentrations existed between sites; however, principal component analysis indicated that the distribution of Fe and P was similar in sugar maple xylem, increasing sharply in the outer rings. Ca and Sr were related, declining steadily from the pith to the cambium, whilst the distribution of Mg, K and Mn was similar by having no radial trend in sugar maple xylem.

Forms of Cu, Ni, and Zn in soils of Sudbury, Ontario and the metal concentrations in plants

Forms of Cu, Ni, and Zn in the contaminated soils of the Sudbury mining/smelting district were studied to assess metal mobility and plant availability. Soil, tufted grass (Deschampsia caespitosa (L.) Beauv.), tickle grass (Agrostis scabra Willd.), dwarf birch (Betula pumila L. var. glandulifera Regel) and white birch (Betula paprifera Marsh.) leaf and twig samples were taken from 20 locations around three Cu-Ni smelters. The sampling sites were collected to cover a wide range of soil pH and soil Cu and Ni concentrations. The water-soluble, exchangeable, sodium acetate-soluble, and total concentrations of the metals in the soils were analyzed. The soils were contaminated with Cu and Ni up to 2000 µg g−1. Zinc concentrations were also elevated in some samples above the normal soil level of 100 µg g−1. The mobility of Cu and Zn, expressed as the proportion of metals in Fl and F2 forms, increased with soil pH decrease. A strong positive correlation was found between the soil exchangeable (F2) Ni and the soil pH. Concentrations of Cu and Ni in birch twigs showed a good linear relationship with exchangeable forms of the metals in soils. A highly significant correlation was also found between total Ni in soils and the metal content of the twigs. No significant correlation was found between Zn concentrations in the soils and plants. Birch twigs are a good indicator (better than leaves) of Cu and Ni contamination of the Sudbury soils. The mobile forms of Cu and Ni and low pH seem to be the main factors that will control the success of revegetation. Strong variability of the soil metal mobility requires any reclamation effort be site-specific.

A COMPARISON OF TEMPORAL PATTERNS IN TRACE METAL CONCENTRATION IN TREE RINGS OF FOUR COMMON EUROPEAN TREE SPECIES ADJACENT TO A Cu-Cd REFINERY

Metal processing at a Cu-Cd refinery at Prescot in N.W. England has led to severe contamination of the surrounding soils and vegetation, although Cu and Cd in bulk deposition declined dramatically between 1975 and 1990. Despite high spatial and temporal variability in metal deposition, mean Cd concentrations in annual tree rings of sycamore (Acer pseudoplatanus L.), lime (Tilia europaea L.) and beech (Fagus sylvatica L.) at Prescot were correlated with annual bulk Cd deposition. In contrast, mean Cd concentrations in ash (Fraxinus excelsior L.) were unrelated to Cd deposition and there was no significant relationship between mean Cu concentrations in tree rings and Cu deposition in any species. Mean Pb concentrations in sycamore, lime and beech at Prescot and the reference site also decreased over time. At Prescot however, Cd concentrations in tree rings formed in the mid 1990s were up to 10-fold higher than the reference site despite Cd deposition values during this period that were typical of levels expected for urban areas in the UK. The high Cd concentrations in wood during this period indicate that the majority of Cd in tree rings at Prescot is derived from soil, limiting the usefulness of dendrochemistry for monitoring temporal changes in metal deposition. It appears that trees are not simply passive recorders of metal deposition and other possibilities, in addition to decreasing atmospheric deposition, may explain the patterns of Cd and Pb found in sycamore, lime and beech. More research on the physiology of metal cycling in trees is required before dendrochemical techniques can be applied with confidence in environmental monitoring programs.

Biological recovery of two previously acidified, metal-contaminated lakes near Sudbury Ontario, Canada

Studies are reported on two small lakes at Sudbury, Ontario located close to a nickel-copper smelter which closed in 1972. At that stage, Baby Lake had a pH of 4.0–4.2 while the adjacent Alice Lake had a pH 5.9–6.3. Both lakes were almost entirely devoid of algae and had neither Zooplankton nor fish. Soon after the closure of the smelter, with its large airborne volume of sulphur dioxide and of copper and nickel containing particulates, the chemistry of the lakes began to change. By 1985, Baby Lake had changed from pH 4.0 to 6.8 and is now at pH 7.2. The pH of Alice Lake increased from a low of 5.9 in the early 1970s to 6.9–7.4 in the mid 1980s and is now at 7.3. Copper and nickel concentrations also decreased in both lakes during this period. The first biota found in the lakes in the post-smelter stage in the early 1980s were benthic red chironomids, planktonic rotifers, and a limited number of phytoplankton species, of which Rhizosolenia was the most common. By the 1990s, 13 phytoplankton species were present in each lake, with a substantial Zooplankton fauna (14 species) of rotifers, copepods, and cladocerans. There are now numerous insect larvae in the sediment and some small fish in both lakes. The biological recovery, which followed substantial reductions in acidity and in soluble nickel and copper concentrations in the waters, is a slower process than chemical recovery and is initially characterized by the dominance of a few species.

Identification and quantification of glutathione and phytochelatins from Chlorella vulgaris by RP-HPLC ESI-MS/MS and oxygen-free extraction

AbstractPhytochelatins are short, cysteine-containing, detoxification peptides produced by plants, algae, and fungi in response to heavy metal exposure. These peptides auto-oxidize easily. Current extraction protocols do not adequately address losses of phytochelatins because of their oxidation and the use of indirect methods for quantification. Method enhancements include the use of an argon environment during extraction to reduce auto-oxidation, the use of glycine-13C2-labeled glutathione as an internal standard, and an electrospray ionization source with a triple quadrupole mass spectrometer as a detector. The method-detection limits were 0.081xa0μM for glutathione, 0.440xa0μM for phytochelatin 2, and 0.120xa0μM for phytochelatin 3. These detection limits were comparable to similar studies and were not compromised incorporating these adjustments. The use of a labeled internal standard and an inert gaseous environment during sample preparation greatly improved calibration linearity and sensitivity. Furthermore, phytochelatin degradation was significantly reduced and more accurately tracked. Previous studies involving phytochelatin analyses have likely been subject to higher variability caused by this propensity for phytochelatins to degrade rapidly in air. The method adjustments were simple and cost-effective and allowed phytochelatin analyses to be performed for hours at a time with minimal auto-oxidation.n FigureThis figure was created using Adobe Photoshop CS3 (San Jose, CA). It displays an image of a chromatogram from our manuscript (a phytochelatin extraction) overlaid upon an image of Chlorella vulgaris and laboratory equipment and materials used in our methods.

Lead dynamics in the forest floor and mineral soil in south-central Ontario

Recent studies have suggested that the residence time of Pb in the forest floor may not be as long as previously thought, and there is concern that the large pulse of atmospheric Pb deposited in the 1960s and early 1970s may move rapidly through mineral soils and eventually contaminate groundwater. In order to assess Pb mobility at a woodland (JMOEC) in south-central Ontario, a stable Pb isotope tracer 207Pb (8u2009mgu2009m−2) was added to the forest floor in white pine (Pinus strobus) and sugar maple (Acer saccharum) stands, respectively, and monitored over a 2-year period. Excess 207Pb was rapidly lost from the forest floor. Applying first-order rate coefficients (k) of 0.57 (maple) and 0.32 (pine) obtained from the tracer study, and estimates of Pb deposition in the region, current predicted Pb concentrations in the forest floor are 1.5–3.1 and 2.1–5.8u2009mgu2009kg−1 in the maple and pine plots, respectively. These values compare favorably with measured concentrations (corrected for mineral soil contamination) of 3.1–4.3u2009mgu2009kg−1 in the maple stand and 2.6–3.6u2009mgu2009kg−1 in the pine stand. The response time (1/k) of Pb in the forest floor at the sugar maple and white pine plots was estimated to be 1.8 and 3.1 years, respectively. The rapid loss of Pb from the forest floor at the JMOEC is much greater than previously reported, and is probably due to the rapid rate of litter turnover that is characteristic of forests with mull-type forest floors. In a survey of 23 forested sites that border the Precambrian Shield in south-central Ontario, Pb concentrations in the forest floor increased exponentially with decreasing soil pH. Lead concentrations in the forest floor at the most acidic survey sites, which exhibited mor-type forest floors, were approximately 10 times higher (∼80u2009mgu2009kg−1) than at the JMOEC, and pollution Pb burdens were up to 25 times greater. Despite the rapid loss of Pb from the forest floor at the JMOEC, the highest pollution Pb concentrations were found in the upper (0–1u2009cm) mineral soil horizon. Lead concentrations in the upper 30u2009cm of mineral soil were strongly correlated with organic matter content, indicating that pollution Pb does not move as a pulse down the soil profile, but instead is linked with organic matter distribution, indicating groundwater contamination is unlikely.