For the routine determination of metals in environmental samples, we require microwave-assisted digestion methods that yield 'total' or 'near-total' recoveries while avoiding the use of HF acid. As inductively coupled plasma mass spectrometry (ICP-MS) is the method of detection, it is desirable to minimize the use of HCl to avoid spectral interferences caused by high Cl- concentrations. Using certified reference materials, we performed a series of modifications to the US EPA method 3051 which included: increasing the temperature and durations of microwave digestion, varying the ratio of sample mass to acid volume, and alterations to the compositions of the acid digestion mixture. The experiments were conducted using urban particulate matter (NIST-1648), coal fly ash (NBS-1633) and six CANMET certified reference materials (Till-2, Till-3, Till-4, LKSD-1, LKSD-2 and LKSD-4), in two laboratories (Health Canada and Environment Canada) using different microwave digestion systems and different ICP-MS instruments. Our modified microwave-assisted nitric acid digestion method improved recoveries for Pb, Zn, V, Fe and Cu approaching 'total' recoveries in the same matrices determined using X-ray fluorescence (XRF) and instrumental neutron activation analysis (INAA) as reported in the certificates of analysis. Recoveries for other elements such as Cr and Ni compared well with 'near-total' recoveries yielded by traditional (non-assisted) acid digestion methods.

The roles of ectomycorrhizal fungi and bacteria associated with corresponding fungal species in distribution of heavy metals within roots and shoots of inoculated pine (Pinus sylvestris L.) seedlings were determined in this study. The mycorrhizal fungi forming different morphotypes were identified by PCR-RFLP using respective primers for an internal spacer transcribed region (ITS) of fungal rDNA. Amongst five fungal species detected, three were identified as Scleroderma citrinum, Amanita muscaria and Lactarius rufus. These fungi used for inoculation of pine seedlings significantly reduced translocation of Zn(II), Cd(II) or Pb(II) from roots to shoots, and the pattern of metal-accumulation was dependent on the fungal species. Ectomycorrhizae-associated bacteria identified as Pseudomonas were used as an additional component of the pine inoculation. These dual root inoculations resulted in higher accumulation of the metals, especially Zn(II), in the roots compared to the inoculation with fungal species alone. Consequently, dual inoculation of pine seedlings could be a suitable approach for plant protection against heavy metals and successful planting of metal-polluted soils.

Plant uptake is a major pathway by which toxic metals can enter the food chain. In this laboratory study we grew spinach, radish, and perennial ryegrass on sand blends containing 50% waste foundry sand (WFS) to assess the availability of Al, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, V, and Zn. The WFSs utilized in this study were from aluminum, iron, and steel foundries. Although there were differences in the amounts of metals accumulated by the various plant species, excessive amounts of heavy metals were not taken up, regardless of WFS treatment. In spinach and radish, B, Cu, Fe, Mn and Zn were found to be within or close to the sufficiency range for agronomic crops. In ryegrass cuttings at 27, 57, and 87 days, Cu and Zn were within sufficiency ranges, but plants were Fe deficient and contained elevated concentrations of B, Mn, and Mo. Data from this study will be useful for state regulatory agencies interested in developing beneficial use regulations for WFSs.

To obtain basic information for evaluating critical levels of O₃ under different nitrogen loads for protecting Japanese beech forests, two-year-old seedlings of Fagus crenata Blume were grown in potted andisol supplied with N as NH₄NO₃ solution at 0, 20 or 50 kg ha-¹ year-¹ and exposed to charcoal-filtered air or O₃ at 1.0, 1.5 and 2.0 times the ambient concentration from 16 April to 22 September 2004. The O₃ induced significant reductions in the whole-plant dry mass, net photosynthetic rate at 380 μmol mol-¹ CO₂ (A ₃₈₀), carboxylation efficiency (CE) and concentrations of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) and total soluble protein (TSP) in the leaves. The concentrations of Rubisco and TSP were negatively correlated with the concentration of leaf acidic amino acid, suggesting that O₃ enhanced the degradation of protein such as Rubisco. The N supply to the soil did not significantly change the whole-plant dry mass and A ₃₈₀, whereas it significantly increased the CE and concentrations of Rubisco and total amino acid. No significant interactive effects of O₃ and N supply to the soil were detected on the growth, photosynthetic parameters and concentrations of protein and amino acid in the leaves. In conclusion, N supply to the soil at <=50 kg ha-¹ year-¹ does not significantly change the sensitivity to O₃ of growth and net photosynthesis of Fagus crenata seedlings.

The dynamics of macroalgal communities and the impact of sewage on their growth were studied in the tidal zone around Zhanqiao Pier of the Qingdao coastal area, in the northwest of the Yellow Sea, China, from September 2001 to September 2003. The tidal zone of the study area is divided into western and eastern sections by the Zhanqiao Pier. Inorganic nitrogen and phosphorus in seawater showed higher concentrations on the eastern side of Zhanqiao Pier than on the western side, because a sewer drains into the eastern side. The macroalgal communities on each side of the Pier showed an obvious difference due to the effect of this sewage discharge. A total of 47 macroalgal species including 10 greens, 11 browns and 26 reds was identified in this study. The species composition and biomass indicated higher values in the nutrient-rich area on the eastern side of Zhanqiao Pier compared with the nutrient-poor area on the western side of Zhanqiao Pier. Some ephemeral and filamentous species dominated seasonally on the eastern side of Zhanqiao Pier, in contrast to the western side where slow-growing species dominated throughout the year. Nutrient gradients and temperature were considered the main factors affecting the distribution of macroalgae communities in time and space. The results are consistent with the common observation that nutrient-poor areas are dominated by slow-growing rather than ephemeral algal species. Moreover, the species diversity in the whole study area had declined when compared to previous records.

The effects of harvesting on the long-term mass balances of calcium (Ca), magnesium (Mg) and potassium (K) were evaluated on a regional level in Sweden. A new high-resolution weathering database was used together with estimates of total deposition, losses through harvest and leaching. Estimates were made for pine and spruce separately and for two harvesting intensity scenarios: stem harvesting and whole-tree harvesting. The mass balance calculations showed net losses of Ca and Mg in almost the whole country for both scenarios. The losses were smaller for pine than for spruce. The K balances were mainly positive for pine but negative for spruce. Leaching was a main factor in the mass balances, especially for Ca and Mg. Whole-tree harvesting in spruce forests led to substantially higher net losses of K and Ca than stem harvesting, according to the calculations. In the whole-tree harvesting scenario in spruce forests the estimated yearly net losses of Ca, Mg and K corresponded to at least 5%, 8% and 3% of the pools of exchangeable base cations, respectively, at 25% of the analysed sites. If losses of this magnitude continue the depletion of the pools of Ca, Mg and K may lead to very low base saturation of the soils, possibly accompanied by negative effects on soil fertility, runoff water quality, tree vitality and tree growth within a forest rotation in parts of Sweden. Avoiding whole-tree harvesting can improve the situation substantially for K, but the losses of Ca and Mg will still be significant.

We studied the effects of liming on fish and crustaceans in a watershed which is in a region known to have one of the highest diversity of aquatic biota in Norway. This watershed, Enningdal, is shared between Norway (1/3) and Sweden (2/3) and includes 61 lakes > 1.0 ha in Norway. Liming started on a large scale in the 1980s. Currently, a total of 26 of lakes (43%) are limed, covering 93% of the total lake area. The mean value ± S.D. of pH and the concentration of inorganic labile Al in these lakes is 6.62 ± 0.35 and 3 ± 4 μg l-¹, respectively. Historical data of fish communities have been obtained from surveys, while test-fishing and sampling of crustaceans were conducted in 24 lakes in recent years (2002-2004). The present study shows that crustaceans to a greater extent than fish has responded to improved water quality after more than 20 years of liming. Of a total of 120 fish populations, 42 (35%) have gone extinct. Only five of the lost fish populations (12%) have been re-established, all due to human re-introductions. Physical barriers are considered to be the main factor preventing fish from invading limed lakes. In contrast, crustaceans have been re-established in most limed lakes. This may be mainly due to their good spreading capacity. However, they might also have survived in refuges within the watershed, or as resting-eggs in the sediment.

We used laboratory experiments to investigate surface resistance (R c) to dry deposition of ozone (O₃) on different types of soil samples collected from the arid deserts and the Loess Plateau of northern China. Furthermore, we measured the factors that affected R c, which depends on the physical and chemical interaction between trace constituents and the deposition surface, and evaluated deposition velocity (V d). There was little influence of geometric surface area, soil weight, or O₃ concentration on V d of O₃. The effect of relative humidity (RH) (i.e. moisture content of the soil) on O₃ uptake was in agreement with results reported in the literature: a distinct RH dependence of V d and little uptake under water-saturated conditions were observed. R c values for all the soil samples examined were in the range 0.21-3.3 s mm-¹ and were exponentially related to the surface area of the particles and the organic carbon content of each soil sample at RH of both <10 and 60%.

In order to test the hypothesis of aluminium toxicity induced by acid deposition, an experimental acid irrigation was carried out in a mature Norway spruce stand in Southern Germany (Höglwald). The experiment comprised three plots: no irrigation, irrigation (170 mm a-¹), and acid irrigation with diluted sulphuric acid (pH of 2.6-2.8). During the seven years of acid irrigation (1984-1990) water containing 0.43 molc m-² a-¹ of protons and sulphate was added with a mean pH of 3.2 (throughfall + acid irrigation water) compared to 4.9 (throughfall) on both control plots. Most of the additional proton input was consumed in the organic layer and the upper mineral soil. Acid irrigation resulted in a long lasting elevation of sulphate concentrations in the seepage water. Together with sulphate both aluminium and appreciable amounts of base cations were leached from the main rooting zone. The ratio between base cations (Ca + Mg + K) and aluminium was 0.79 during acid irrigation and 0.92 on the control. Neither tree growth and nutrition nor the pool of exchangeable cations were affected significantly. We conclude that at this site protection mechanisms against aluminium toxicity exist and that additional base cation runoff can still be compensated without further reduction of the supply of exchangeable base cations in the upper mineral soil.

This paper reports the effect of using coarse substrates in the upper layer of a gravel-based tidal flow reed bed treating pig farm wastewater. The aim of this unconventional medium arrangement is to seek a solution for the problem of clogging that frequently takes place during the treatment of strong wastewaters. Results from lab-scale experiments demonstrated that, in general, employing coarse substrates in the upper layer of the reed bed gave greater efficiency for the removal of organic matter and suspended solids, due to reduced clogging. A specific clogging tendency rate was defined to quantitatively describe the clogging behaviour. Calculation of the tendency rate revealed that the unconventional medium arrangement had a clear advantage over the conventional arrangement of employing fine gravel or sand in top layer.