Industrialization and urbanization along the coastal population centers have brought great changes in the land cover and material fluxes from watersheds to receiving bays and estuaries. We have embarked a multiyear research project on “Watersheds Nutrient Loss and Eutrophication of Jiaozhou Bay” for the period of 2000 to 2004, funded by the Natural Science Foundation of China to examine human influence on the marine sector of ecosystem. Jiaozhou Bay, located in the southern part of Shandong Peninsula, was selected because of the existence of long-term hydrographic and meteorological records since the 1930s and recent observations on the marine ecological variables. We have made extensive and periodic measurements on the water movement, nutrients, phytoplankton, and microbe in water column and bottom sediments. Box and 3-dimensional hydrodynamic models were developed and utilized to understand the evolution of eutrophic status with time. It was found that primary productivity has suffered from silica depletion followed by phosphate, and the dominance of large phytoplankton has been replaced by small-size communities. These ecosystem changes were brought by the changes in the relative contribution among major pathways and concentrations, owing to the human activities in the watershed. Eight articles in this volume reported various aspects of the linkage between watershed human activities and ecosystem for the Jiaozhou Bay as the initial outcome of this project.

The health of near shore marine ecosystems has long been a concern because of its importance to coastal areas. Jiaozhou Bay (JZB) is one such marine ecosystem experiencing rapid water quality degradation in the last several decades. From the area surrounding the bay, the nutrients discharged into the bay through surface water and groundwater has been greatly changed. The thickness of the aquifers and the permeability is relatively high, the concentrations of nutrients in the groundwater are generally high, and so the groundwater discharged into JZB is very significant. However, no attempt has ever been made to evaluate the amount of nutrients discharged into the bay area via groundwater. In this study, the cross-section method and water balance method were used to estimate the amount of groundwater and nutrients discharged into JZB via the subsurface. Groundwater was monitored and sampled at aquifers surrounding the bay area, and some previously available data was also analyzed. The results indicated that groundwater from the Baisha Aquifer east of JZB now is the major source of nutrients (nitrate, dissolved SiO₂) being discharged into the bay. The concentrations of nutrients in the groundwater have been increasing with intensive agricultural land use. However, Dagu Aquifer, the largest aquifer north of JZB, only provides limited nutrients to the bay area because of the construction of a low permeability subsurface dam. Historically, during the 1970s to the 1990s, the Baisha Aquifer experienced seawater intrusion due to excessive groundwater withdrawal. The same was true for the Dagu Aquifer from the 1980s to the 1990s. Because of this, no significant nutrients were discharged into the bay.

Emissions of sulphur and oxidized nitrogen compounds in Europe have been reduced following a series of control measures during the last two decades. These changes have taken place during a period in which the primary gases and the wet deposition throughout Europe were extensively monitored. Since the end of the 1970s, for example land based sulphur emissions declined by between 90 and 70% depending on the region. Over the same period the total deposition of sulphur and its partitioning into wet and dry deposition have declined, but the spatial pattern in the reduction in deposition differs from that of emission and has changed with time. Such non-linearities in the emission-deposition relationship are important to understand as they complicate the process of assessing the effects of emission reduction strategies. Observed non-linearities in terrestrial sulphur emission-deposition patterns have been identified in north west Europe due to increases in marine emissions, and are currently slowing the recovery of freshwater ecosystems. Changes in the relative amounts of SO₂ and NH₃ in air over the last two decades have also changed the affinity of terrestrial surfaces for SO₂ and have therefore changed the deposition velocity of SO₂ over substantial areas. The consequence of this effect has been the very rapid reduction in ambient SO₂ concentration in some of the major source areas of Europe, where NH₃ did not change much. Interactions between the different pollutants, generating non-linearities are now being incorporated in long-range transport models to simulate the effects of historical emission trends and to provide projections into the future. This paper identifies non-linearities in emission deposition relationships for sulphur and nitrogen compounds in Europe using data from the EMEP long-rang transport model and measured concentration fields of the major ions in precipitation and of SO₂ and NO₂ in surface air.

A complete record derived from the core from the Daihai Lake in a remote area provides new insights into the changing atmospheric heavy metal deposition associated with historical industrial activities, the Asian monsoon, long-range transport, and the chemical composition of matter derived from weathering of catchment. The fluctuation of lithogenic element concentration in the lake sediments can readily be explained by a particle sorting effect induced by the Asian monsoon. The variation of atmospheric deposition of Cu and Pb shows a similar profile in the lower part of the core sediments, and coincides with environmental change, with high atmospheric deposition coupled with wet, temperate period; while low deposition with dry, cold period, indicating a transport variation of heavy metal pollutants entrained by the Asian summer monsoon. From the beginning of nineteenth century, the atmospheric deposition of Cu and Pb decreased and then slowly increased. This may be associated with the destroyed industry induced by long-term wars in China and the less heavy metal pollutants relative to the weak Asian summer monsoon in this period. Comparison between atmospheric-derived metal and sediment trap metal using Ga as the reference element shows that atmospheric Cu and Pb budgets do not exceed the fluvially-induced Cu and Pb budgets in the indirectly disturbed area. On average, there have been approximately 5.4 mg m-² yr-¹ of Cu and 5.1 mg m-² yr-¹ of Pb atmospherically deposited in the region.

Rapid field-based screening methods for the semi-quantitative determination of heavy metals are desirable to support the increasing demand for the rapid characterization of contaminated sites. Single-use sensors have been fabricated using low-cost screen-printing (thick film) technology. These electrodes, coupled with differential pulse anodic stripping voltammetry (DPASV), have provided a rapid, inexpensive on site screening device for the simultaneous field-based determination of cadmium (Cd) and lead (Pb) in soil and water samples in the microgram per litre/kilogram range. A simplified soil extraction procedure, using 1 mol l-¹ aqua regia and a 3 min ultrasonic sample agitation, has been developed to allow field-based device usage. Extraction efficiency was evaluated using a soil certified reference material (CRM). Recoveries of 64% and 52% for Cd and Pb respectively were obtained, with a relative standard deviation (RSD) of <8% for both analytes (n = 10). Soil samples (82) were tested using the combined extraction-DPASV procedure and compared against standard ICP-AES analysis. Correlation coefficients of 0.9782 and 0.9728 for Cd and Pb respectively demonstrate good correlation between methods. Analytical data is also reported for copper (Cu), but significant peak distortions reduce the confidence of the method for this metal. Results indicate that the combined extraction-DPASV method yields semi-quantitative data for rapid field-based site screening purposes.

Extensive measurements were made using an Aerodyne quantum cascade laser absorption spectrometer (QCLAS) to study the diurnal and seasonal cycles of NH₃ concentrations in Manchester city centre. Measurements made at rooftop levels showed traffic to be a significant source of NH₃ concentrations in the winter. This was illustrated by a bimodal diurnal cycle of NH₃ concentrations that was synchronized with traffic, and also by a correlation with NOx, a traffic related pollutant. These patterns were not observed during the summer, suggesting other sources become more important. Measurements were also made at street level during winter and summer, close to the traffic source. This time the contribution from traffic was also observed in the summer, albeit weaker. Enhanced NH₃ concentrations were often seen in winds from the southwest that could not be related to local sources, suggesting that ambient concentrations in the city are strongly influenced by sources outside the city. It is estimated that the total NH₃ emission from the city centre is between 0.7 and 2.3 t km-² year-¹.

Ammonia (NH₃) emission from nitrogen (N) fertilizers used in agriculture decreases N uptake by the crop and negatively impacts air quality. In order to better understand the factors influencing NH₃ emission from agriculture, this research was conducted with four major soils used for potato production: Biscayne Marl Soil (BMS, pH 7.27), and Krome Gravelly Loam (KGL, pH 7.69) from Florida; and Quincy Fine Sand (QFS, pH 6.65), and Warden Silt Loam (WSL, pH 6.46) from Washington. Potassium nitrate (KNO₃), ammonium nitrate (NH₄NO₃), ammonium sulfate ((NH₄)₂SO₄) or urea ((NH)₂CO) sources were evaluated for ammonia volatilization at 75 kg N ha-¹ rate. The soil water regime was maintained at either 20 or 80% of field capacity (FC), and incubated at 11, 20 or 29°C. Results indicated that NH₃ volatilization rate at 20% FC was 2 to 3-fold greater than that at 80% FC. The cumulative volatilization loss over 28 days ranged from 0.21% of N applied as NH₄NO₃ to 25.7% as (NH₄)₂SO₄. Results of this study demonstrate that NH₃ volatilization was accelerated at the low soil water regime. Moisture quotient (Q) is defined as a ratio of NH₃ emission rate at 20% FC to that at 80% FC both at the same temperature. The peak Q values of NH₃ volatilization were up to 20.8 for the BMS soil at 20°C, 112.9 for the KGL soil at 29°C, 19.0 for the QFS soil at 20°C, and 74.1 for the WSL soil at 29°C, respectively. Thus, maintaining a suitable soil water regime is important to minimize N-loss via NH₃ volatilization and to improve N uptake efficiency and air quality.

The bursting of the mining dam of Aznalcollar (Seville, Spain) triggered an increase in the concentration of heavy metals in the soils of the river Guadiamar valley as a result of the leaching of the pyritic sludge deposited on them. After the cleaning operations which included, as well as mechanical clearing, the addition of different amendments, some areas with residual sludge remained, from which some heavy metals are being mobilized by the cyclical recharge and discharge processes of water in the profiles. This paper analyzes the effect of the soil recovery operations and the climatology on the concentration of metals and their distribution in the soil profile in an area affected by the toxic spill. Fourteen points have been selected in a plot in which acidity persists, there is no vegetation, and residual sludge stains can be seen at a glance. The temporal and spatial evolution of the extractable metals: Fe, Cu, Mn and Zn, the pH and the oxidable fraction has been measured in-depth. The results obtained up to now indicate a leaching of the pollutant towards deeper horizons, finding, at a depth of 757 cm, pH values of 3.5 and very high Fe and Mn concentrations available, especially in the profiles with large sized pores, with a big fraction of sand. On the surface, seasonally, there are low pH values of around 2.5 and extractable Fe contents of over 4000 ppm, which might have an influence on the quality of surface runoff or underground water.

High mortality rates due to predation from fish may reduce densities of preferred prey animals. Predation may also depress the rate of recovery from environmental stress. In an alpine ecosystem damaged by acidification, we compared three different techniques of monitoring the recovery of two large species of crustaceans, the amphipod Gammarus lacustris and the notostrachan Lepidurus arcticus. The methods used were: (1): benthic littoral kick samples, (2): artificial substrate in the form of jute bags, (3): examination of brown trout stomachs. The monitoring took place in two limed lakes at the Hardangervidda mountain plateau in Central Norway, L. Svartavatn and L. Svartavasstjørni. Brown trout, Salmo trutta, is the only fish species in the lakes. Liming as a water quality improvement measure was started in 1994. All stomach samples were negative with respect to Gammarus and Lepidurus during the period 1987-1998. In 1999, the first records of both species were done in trout stomachs collected from Lake Svartavatnet. In Lake Svartavasstjørni, Lepidurus and Gammarus reappeared in fish stomachs in 2001 and 2002, respectively. During the period of monitoring, no records of these crustaceans were done in benthic samples and on artificial substrate in any of the two lakes. In an unacidified reference site, Lake Skiftesjøen, both benthic samples and the jute bags indicated a dense population of Gammarus. Our results strongly indicate that studies of fish stomachs are the best method for monitoring low-density populations of attractive fish food animals.

The long-term monitoring of precipitation and its chemical composition are important for identifying trends in rain quality and for assessing the effectiveness of pollution control strategies. A statistical test has been used to the atmospheric concentrations measured in the French rural monitoring network (MERA) in order to bring out spatio-temporal trends in precipitation quality in France over the period 1990-2003. The non-parametric Mann-Kendall test which has been developed for detecting and estimating monotonic trends in the time series was used and applied in our study at annual values of wet-only precipitation concentrations. The emission data suggest that SO₂ and NO x emissions decreased (-3.3 and -2.0% year-¹, respectively) contrary to NH₃ emissions that increased slightly (+0.2% year-¹) over the period 1990-2002 in France. On the national scale, the pH values have a significant decreasing trend of -0.025 ± 0.02 unit pH year-¹. [graphic removed] and [graphic removed] concentrations in precipitation have a significant decreasing trend, -3.0 ± 1.6 and -3.3 ± 0.6% year-¹, respectively, corresponding with the downward trends in SO₂ emissions in France (-3.3% year-¹). A good correlation (R ² = 0.84) between SO₂ emissions and [graphic removed] concentrations was obtained. The decreasing trend of [graphic removed] was more significant (-5.4 ± 5.2% year-¹) than that of [graphic removed] (-1.3 ± 2.4% year-¹). Globally, the concentration of the major ions showed a clear downward trend including marine and alkaline ions. In addition, the relative contribution of HNO₃ to acidity precipitation increased by 51% over the studied period.