In a step-by-step exercise - beginning at full greenhouse gas accounting (FGA) and ending with the temporal detection of emission changes - we specify the relevant physical scientific constraints on carrying out temporal signal detection under the Kyoto Protocol and identify a number of scientific uncertainties that economic experts must consider before dealing with the economic aspects of emissions and their uncertainties under the Protocol. In addition, we answer one of the crucial questions that economic experts might pose: how credible in scientific terms are tradable emissions permits? Our exercise is meant to provide a preliminary basis for economic experts to carry out useful emissions trading assessments and specify the validity of their assessments from the scientific point of view, that is, in the general context of a FGA-uncertainty-verification framework. Such a basis is currently missing.

The distributions and biogeochemical cycles of arsenic in the aquatic environment have captured the interest of geochemists due to arsenic's multiple chemical forms, the toxicity of certain arsenic species and large anthropogenic input. Seasonal variations in the dissolved inorganic arsenic concentration and speciation in Jiaozhou Bay, which is located on the west coast of the Yellow Sea in northern China, are presented here. Three cruises were carried out in Jiaozhou Bay under varying tidal regimes, one at neap tide and one at spring tide in August and one at spring tide in October of 2001. In addition to the transect surveys, the main sources of dissolved inorganic arsenate and arsenite in Jiaozhou Bay, including riverine input from five major tributary rivers, atmospheric dry and wet depositions, and groundwater and wastewater input, were collected in different seasons to estimate arsenic transport through different sources. The mean concentrations of total dissolved inorganic arsenic (TDIAs, As (V+III)) in Jiaozhou Bay were statistically comparable between summer and autumn, with higher concentrations at the northwest and northeast parts of the bay, reflecting human activities. The As (III)/TDIAs ratio ranged between 0.045 and 0.68, with an average of 0.16, implying that arsenate was the dominating species in Jiaozhou Bay. A preliminary box model was established to estimate the water-mass balance and arsenic budgets for Jiaozhou Bay, which demonstrated that river inputs and atmospheric depositions were the main sources of arsenic into Jiaozhou Bay. The concentrations of dissolved inorganic arsenic in Jiaozhou Bay have decreased in the last two decades. Compared with other areas in the world, the concentration of arsenic in Jiaozhou Bay remains at the natural level and this region can be characterized as a less disturbed area.

The recovery from acidification has led to the demand for more precise criteria for classification of acidification. The Swedish Environmental Protection Agency has revised Sweden's Ecological Quality Criteria for acidification to improve the correlation between the chemical acidification criteria and biological effects. This paper summarises the most relevant findings from several of the studies commissioned for this revision. The studies included data on water chemistry in 74 reference lakes in southern Sweden with data on fish in 61 of the lakes, as well as data on littoral fauna in 48 lakes. We found that the acidity variable most strongly correlated to the biota was the median pH from the current year. Our results probably do not reflect the mechanisms behind the negative effects of acidity on the biota, but are fully relevant for evaluation of monitoring data. The biogeochemical models used for predicting acidification reference conditions generate a pre-industrial buffering capacity. In order to get an ecologically more relevant criteria for acidification based on pH, we transferred the estimated change in buffering capacity into a corresponding change in pH. A change of 0.4 units was defined as the threshold for acidification. With this criterion a considerably lower number of Swedish lakes were classified as acidified when compared with the present Ecological Quality Criteria.

Pollution of the atmosphere with cadmium (Cd), mercury (Hg), and lead (Pb) is a consequence of human activities. Natural archives are necessary to reconstruct the long-term history of metal deposition because accurate measurement of atmospheric deposition is a recent accomplishment. Reconstructions require: (1) accurate determination of concentrations of elements and isotopes, (2) accurate chronology of archives, and (3) archives that faithfully record atmosphere deposition. The most useful long-term archives are accumulations of ice and snow, peat, and lake sediment. Quantification of Cd deposition is uncommon because of its low concentration and substantial chemical mobility. Nonetheless, trends in peat and lake sediment are similar to those of Hg and Pb since ca. 1800 a.d. Both Hg and Pb are relatively chemically immobile and thus the peat and lake archives are believed to record historic trends of atmospheric deposition. Isotopic and concentration studies of Pb indicate a history of northern hemisphere atmospheric pollution extending back prior to 0 a.d. Although measurements of Hg concentration are now routine, isotopic measurements are in their infancy. Some Hg pollution sources have unique isotopic ratios, thereby contributing unique signals to the total Hg. Maximum accumulation rates of Hg and Pb occur up to 10 years later than for Cd (1970s versus 1960s in eastern North America, perhaps slightly later in Europe). By 2004, deposition of Cd, Hg, and Pb had declined from peak values in eastern North America more than 75, 75, and 90%, respectively.

In order to achieve remediation of contaminated substrates, phyto-extraction in pot experiments utilizing lettuce seedlings as universal accumulator plants was investigated. As test substrates, mine tailings from Shiheung and Okdong mines in Korea (particularly high in Pb, Zn, Cu, and Cd), as well as samples from historic mining site at Oberzeiring in Austria (particularly high in Pb, Sb and As) were used, and compared with adjacent farmland soils. After 21 days of growth in the test substrate, the lettuce plants were harvested, and the adjacent soils parted in bulk and root soils. Special soil bacteria, adapted to high Cd levels (Exiguobacter sp.) and capable of adsorbing large amounts of cadmium from solution, as well as perlite (Samson Perlite Inc.) were added to the test substrates before plant growth. Speciation changes in the solids were investigated by sequential leaching, utilizing neutral MgCl₂ (exchangeable), 0.16 M acetic acid, hydroxylamine pH 2, oxalate pH 3, H₂O₂ oxidation, and reflux with aqua regia. Plant growth induced differentiation between root and bulk soils, the differences were more pronounced for the non-contaminated controls. The iron-hydroxide phase increased about 30%, and also the amount of iron-hydroxide bound Be, Cd, Co, Cu, Mg, Mo, Sb and V concentrations, coming mainly from less mobile fractions. The Mn hydroxide phase, however (hydroxylamine), remained rather constant. After plant growth, the root soils were significantly lower in available P, and significantly higher in available Ca, Mn, and Na than the corresponding bulk soils. Addition of Cd-adapted soil bacteria led to a severe decrease of plant yield, but metal uptake changed in both directions. Exchangeable P in both root and bulk soil decreased, and Be, Co, Cr, Fe, K, Li, Mg, Mn, Ni, and Sr in the residual organic fraction increased. This can be interpreted as competition for nutrients, dissolution of residuals by bacterial action, and adsorption to a tightly bound biomass. Addition of perlite hardly affected the plant yield, and again metal uptake changed in both directions, but led to a decrease of siderophilic elements in the Fe- and Mn hydroxides of the bulk soil. In the root soil, perlite addition above all decreased available K, P and As, with respect to the untreated samples. Bacteria addition to perlite treated soils shifted some elements from weak acid mobile towards less available fractions.

Substrates associated with two historic gold mining sites in north Westland, New Zealand, have locally very high arsenic concentrations (commonly 10-40 wt% As). The substrates consist of iron oxyhydroxide precipitates, and processing mill residues. Waters associated with some of these substrates have high dissolved arsenic (commonly 10-50 mg/L As). Natural revegetation of these very high arsenic sites has occurred over the past 50 years, although some areas of substrate remain bare. Revegetating species include native and adventive shrubs, adventive grasses, rushes, and mosses, and native ferns. Revegetation by higher plants follows initial colonization by mosses, and some shrubs are growing directly in high-arsenic substrate. Shrubs, especially manuka (Leptospermum scoparium), gorse (Ulex europaeus), tree fuchsia (Fuchsia excorticata) and broadleaf (Griselinia littoralis) largely exclude arsenic from their shoots (< 10 mg/kg dry weight) irrespective of the As content of the substrate. Likewise, most grasses, and reeds (Juncus spp.), have only modest As contents (typically < 100 mg/kg dry weight). However, mosses growing on high-arsenic substrates have strongly elevated arsenic contents (> 0.2% dry weight). In particular, the moss Pohlia wahlenbergii acts as a hyperaccumulator, with up to 3% (dry weight) As. Antimony (Sb) contents of all plants are about one thousandth of that of arsenic, reflecting the As/Sb ratio of the substrates. Plant establishment in the high-As substrates may be locally limited by low nutrient status, rather than arsenic toxicity. The shrubs, grasses, and reeds identified in this study are arsenic tolerant and largely exclude arsenic from their shoots so that revegetation with these species, can help to isolate the high-arsenic substrates from the surface environment. These species could be used as phytostabilisation agents on high-arsenic sites that are remote from human habitation. In contrast, the mosses, despite their high arsenic tolerance, are a less desirable component of revegetation of high-arsenic substrates because they actively transfer arsenic from the substrate to the biosphere.

Phosphorus (P) release from bottom sediments can be a significant source to the overlying water column, potentially maintaining and enhancing algal growth and eutrophic conditions in lakes and reservoirs. Thus, the objectives of this study were to: (1) measure P flux under aerobic and anaerobic conditions from intact sediment cores collected at Beaver Reservoir, northwest Arkansas, (2) evaluate the spatial variability in measured sediment P flux under aerobic and anaerobic conditions along the reservoir, and (3) compare external and internal P loads to Beaver Reservoir. Six intact sediment cores were collected at three sites representing the lacustrine, transitional, and riverine zones during June 2003, September 2003 and February 2004 and incubated for 21 days in the dark at ~22°C. Three cores from each site were incubated under aerobic conditions and anaerobic conditions. Water samples were collected from the overlying water column in each core daily for the first five days and every other day thereafter and analyzed for soluble reactive phosphorus (SRP). Water removed from the core was replaced with filtered lake water, maintaining a constant overlying water volume of 1 l. Sediment P flux under anaerobic conditions (<0.01-1.77 mg m-² day-¹) was generally greater than that measured under aerobic conditions (<0.01-0.89 mg m-² day-¹). Some spatial variability existed in sediment P flux where P flux was generally greatest at the sites in the riverine and transitional zones. Maximum sediment P flux was observed under anaerobic conditions in cores collected from the transitional zone during September 2003. Average sediment P flux under aerobic conditions (0.09 mg m-² day-¹) and anaerobic conditions (0.31 mg m-² day-¹) was greater than the external P flux (0.05 mg m-² day-¹) estimated from the Beaver Reservoir tributaries. Results showed that the annual internal P load (7 Mg year-¹) from bottom sediments in Beaver Reservoir was less than 10% of the annual external P load (~81 Mg P year-¹). The internal P load was significant, but it would not currently be cost effective to manage this P source given the large surface area of Beaver Reservoir.

A multi-media monitoring field investigation, which included atmospheric, road sediment and soil samples, was carried out at two highway study sites to identify past and present Pb sources. Past Pb anthropogenic sources such as paint and leaded gasoline were linked to significant Pb accumulation in roadside soils at both sites through Pb isotopic analyses. This was achieved by identifying the distinct Pb isotopic composition in older versus newer Pb accumulation at different depths across the soil profile. Older Pb accumulations exhibited lower ²⁰⁶Pb/²⁰⁷Pb isotopic ratios, consistent with Canadian Pb-bearing ores, whereas newer Pb accumulations reflected a mixture of the ²⁰⁶Pb/²⁰⁷Pb ratios of road sediment samples, with the Pb isotopic signature of uncontaminated soil. Isotopic analyses were also helpful in identifying road sediment as an important current source of Pb in roadside soils, by comparing the isotopic signatures derived from road sediment and atmospheric dustfall. The known association of Pb with anthropogenic sources was used to indirectly relate other metals (Cu, Mn, Zn) to the same source by the Enrichment Ratio method. Significant positive correlations at the 90-95% confidence level were found between Cu, Zn and Pb Enrichment Ratios in roadside and dust deposition samples. Weaker correlations were found between Mn and Pb, at the highway study site with the least amount of traffic. However, correlations between these two metals were significant at the 90% confidence level for the busier highway site highlighting Mn potential anthropogenic source. An isotopic tracer study is suggested to further investigate the process of Mn redistribution in the environment due to exhaust fuel emissions. More research is needed regarding the potential impact from using a Mn-based fuel additive.

A geologic classification scheme was combined with elevation to test hypotheses regarding watershed sensitivity to acidic deposition using available regional spatial data and to delimit a high-interest area for streamwater acidification sensitivity within the Southern Appalachian Mountains region. It covered only 28% of the region, and yet included almost all known streams that have low acid neutralizing capacity (ANC ≤20 μeq l⁻¹) or that are acidic (ANC ≤0). The five-class geologic classification scheme was developed based on recent lithologic maps and streamwater chemistry data for 909 sites. The vast majority of the sampled streams that had ANC ≤20 μeq l⁻¹ and that were totally underlainby a single geologic sensitivity class occurred in the siliceous class, which is represented by such lithologies as sandstone and quartzite. Streamwater acid-base chemistry throughout the region was also found to be associated with a number of watershed features that were mapped for the entire region, in addition to lithology and elevation, including ecoregion, physiographic province, soils type, forest type and watershed area. Logistic regression was used to model the presence/absence of acid-sensitive streams throughout the region.

Atmospheric polycyclic aromatic hydrocarbons (PAHs) were determined in particulate matter (PM10) collected in a suburban area with industrial and vehicular emissions in the Metropolitan Area of Rio de Janeiro City (Brazil). A total of 22 samples were collected between March and August 2005 by means of a high volume PM10 sampler. The particulate matter contained in the filters was extracted ultrasonically with dichloromethane. The extracts were later analyzed by gas chromatography coupled to a mass spectrometer (GC/MS). The individual concentrations of PAHs ranged between the detection limit and 0.386 ng m-³. The PAHs concentrations observed in this study were towards the lowest end of the range of values reported for other European locations and also lower than values obtained for South America. PAHs concentrations and molecular ratios showed that light cars seem to be the main contributors to PM10 emissions, but diesel vehicles are clearly minor emission sources and industrial contributions should not be disregarded until more data are obtained.