Shaun A. Watmough

Monitoring historical changes in soil and atmospheric trace metal levels by dendrochemical analysis.

The use of dendrochemistry for monitoring historical changes in trace metal deposition and mobilisation of metals in soils is evaluated. In experimental studies, mobilisation of trace metals in surface soil following deliberate acidification was recorded in sugar maple (Acer saccharum) tree-rings with minimal lateral movement between rings. Furthermore, positive correlations between wood (3 year section 1993-95) and foliar chemistry (mean concentration 1993-95) were found for Cd and Zn, but not for Cu and Ni, showing that mobility up the tree bole differs between metals. Even so, substantial lateral movement of elements between rings occurs in some species. Stable Pb isotope ratios in tree-rings were used to show that sacred fir (Abies religeosa) is not a useful monitor of Pb deposition because Pb accumulates in the heartwood. Numerous sophisticated analytical techniques are now used in dendrochemical studies, including laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry that enable the multi-element analysis of extremely small tree-rings with low detection limits. Clearly, not all tree species are suitable for dendrochemical studies, but if careful sampling strategies are used and suitable tree species are chosen, the chemical analysis of tree-rings can provide information concerning historical changes in soil and atmospheric trace metal levels unavailable from any other source.

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.

Major element fluxes from a coniferous catchment in central Ontario, 1983–1999

Acid deposition over time scales of decades may deplete essential base cation (BC) reserves in soils to the extent that forest health may be affected. In order to assess the nutrient status of soils in central Ontario, input–output budgets for calcium (Ca), magnesium (Mg), potassium (K) and nitrogen (N) were calculated over a 17-year period (1983–1999) for a coniferous catchment in the Muskoka-Haliburton region. Inputs through deposition and weathering (BCs only), were compared with outputs through stream export and net accumulation in forest biomass. Despite a lack of forest growth at PC1, annual NO3–N concentrations in the stream were low (<0.1 mg/l) over the 17-year period, and over 80% of the atmospheric N input was retained in the catchment, indicating this catchment has not reached N-saturation. Stream export of Mg, and in particular Ca, exceeded input of these elements through deposition and weathering, indicating a net loss from the catchment over the 17-year period. Mass balance calculations indicated there was no net loss of K from the catchment. Soil re-sampling measurements confirmed large losses of Ca, but not Mg, and there were significant decreases in both NaCl-exchangeable Ca concentrations and soil pH between 1983 and 1999. The measured decline in soil Ca concentration amounted to a loss of approximately 85 kg/ha Ca from the exchangeable pool over the 17-year period. Similarly, input–output budget calculations indicated a net loss of Ca from the catchment in the range of 76 to 88 kg/ha between 1983 and 1999. Although the magnitude of Ca export decreased over the 17-year period, current stream export continues to exceed Ca input through deposition and weathering.

Recent Changes and Patterns in the Water Chemistry of Lake Simcoe

After the Great Lakes, Lake Simcoe is the largest lake in southern Ontario. Located within a 1 hour drive of half the population of Ontario, there is currently major concern over the impact of rapid urbanization on the nutrient status of the lake. However, despite a more than doubling of the human population in the Lake Simcoe watershed over the past two decades, average total phosphorus (TP) levels were lower in 2000–2003 compared with 1980–1983 at six of eight lake stations, and declines were significant at the most nutrient-enriched near-shore sites located in Kempenfelt Bay (0.29 μg/L/year) and Cooks Bay (0.31–0.41 μg/L/year). Total P concentrations varied two-fold across the lake, and phytoplankton bio-volume followed a similar pattern, with greatest phytoplankton abundance occurring at high TP sites, particularly in Cooks Bay. Nevertheless, steep declines in bio-volume occurred at all sites beginning in the mid-1990s, and water clarity (Secchi disk depth) improved concurrently such that Secchi depths were 40–80% greater in 2000–2003 compared with 1980–1983. Zebra mussels, which became established in Lake Simcoe around 1995, likely contributed to decreased phytoplankton bio-volume and related improvements in water clarity, which began during the mid-1990s. Despite major reductions in phytoplankton bio-volume, average rates of dissolved oxygen (DO) depletion (18 m-bottom zone; normalized to 4°C) did not change substantially over time, and were similar in 2000–2003 (average 1.25 ± 0.21 g O2/m3/month) compared with 1980-1983 (average 1.26 ± 0.19 g O2/m3/month). In contrast, minimum, end-of-summer DO levels (18 m-bottom) increased slightly over the period of record. Although there has been some improvement in end-of-summer DO availability, DO concentrations continue to decline to levels that are limiting to many fish species (e.g., 3.8 mg O2/L in 2001) by the end of the summer stratified period.

Base Cation and Nitrogen Budgets for a Mixed Hardwood Catchment in South-central Ontario

There is growing concern that available base cation pools in soil are declining in eastern North America and that some forests are approaching nitrogen (N) saturation due to the combined effects of acid deposition and harvesting. To assess these concerns, elemental mass balances for calcium (Ca), magnesium (Mg), potassium (K), and N were conducted over a 17-year period in a representative mixed hardwood forest (HP4) in the Muskoka-Haliburton region in central Ontario, Canada. On average, 76% of the N measured in bulk deposition, which is a conservative estimate of total N deposition, was retained in HP4, with tree uptake accounting for over half of the retained N. Year-to-year variations in annual NO3 export were affected by climate variations, although the low annual NO3-N concentrations (80–156 μg/L) suggest that HP4 is not approaching N saturation. Losses of Ca, Mg, and K in stream export plus accumulation in trees (more than 12 cm in diameter at breast height) exceeded inputs in deposition by 296, 76.2, and 53.6 kg/ha, respectively, over the 17-year period. Inclusion of mineral weathering estimates obtained using PROFILE, zirconium (Zr) depletion, and total analysis correlation failed to balance Ca losses from HP4, and calculations indicate that between 98 and 145 kg/ha (depending on mineral weathering estimate) was lost from the soil exchangeable pool between 1983 and 1999. These losses were supported by repeated field measurements, which showed that the exchangeable Ca concentrations and soil pH decreased over the 17-year period, particularly in the upper soil horizons. When mineral weathering estimates are included, mass balance calculations generally indicated that there was no net loss of Mg and K from HP4, which was confirmed by our soil measurements. At present, there is sufficient Ca in the soil exchangeable pool to sustain forest growth at HP4; however, continued losses of Ca due to leaching and harvesting at the present rate may ultimately threaten the health and productivity of the forest within just a few decades.

A dendrochemical survey of sugar maple (Acer saccharum Marsh) in south-central Ontario, Canada

A dendrochemical survey of sugar maple (Acer saccharum Marsh) was conducted insouth-central Ontario, which encompassed twenty-two sites in areas that both exceeded orwere below the published Critical Loads with respect to acid deposition. Areas thatexceeded the Critical Load were located remote from point emission sources, but were alsocharacterized by thin, nutrient-poor soils overlying the Precambrian Shield. ThepHaq of surface soils (A-horizon) was lower at sites on the Precambrian Shield andwater-extractable concentrations of Ca decreased exponentially with decreasing soil pH. Significant polynomial relationships between soil pH and soil Ca and sugar maple growth,assessed as cumulative tree-ring growth between 1949 and 1998, explained 40% and 37% ofthe variation in sugar maple growth respectively, with lowest growth associated with lowsoil pH and low soil Ca. Furthermore, there was a significant linearrelationship between wood Ca concentrations (averaged between 1949 and 1998) and soil pHand concentrations of several trace elements in wood (Mn, Pb, Zn, Cd, Sr and Rb) were greater atlow soil pH. Poor sugar maple growth was associated with low wood Ca concentrations andhigh wood Al levels, which together accounted for 43% of the variation in sugar maplegrowth in a multiple regression model. None of the other wood chemistry variablescontributed significantly to the model. These data suggest that sugar maple grows poorlyon acidic soils with low Ca and high Al levels. Although such acidic podzols occurnaturally in some areas overlying the Precambrian Shield, if Ca losses due to aciddeposition and/or harvesting exceed inputs through weathering and deposition(i.e. exceed Critical Load), sugar maple growth may be adversely affected and ultimately lead toincreased incidence of sugar maple decline.

Dispersal and mobility of heavy metals in relation to tree survival in an aerially contaminated woodland soil

Nearly a century of metal deposition adjacent to a metal refinery in Prescot, north-west England has led to highly elevated metal levels in soils at a dominantly Acer pseudoplatanus woodland, but with incongruously and perplexingly few detrimental effects on trees. Dispersal and speciation of Cu, Cd, Zn, Pb and Ni in soil was found to be extremely variable, but spatial patterns of metals were inter-related and also related to soil pH and soil organic matter. These soil variables were all generally higher in soil directly beneath trees than in soil between trees, and were particularly high beneath the spreading canopy of Aesculus hippocastanum. It is argued that this heterogeneous dispersal and availability of metals in soils may explain the survival of mature trees and the successful establishment of seedlings within the woodland. Differing speciation and mobility has allowed high disappearance rates of metals since recent closure of the refinery, which may result in soil recovery at a faster rate than previously thought.

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.