Joint application of an empirical and mechanistic model for regional lake acidification

The empirical direct distribution model for lake acidification is calibrated for use in an integrated assessment model which predicts the regional impact of an acid deposition control strategy. The calibration is based on the mechanistic Model of Acidification of Groundwater in Catchments (MAGIC). The models are applied jointly to a set of 33 statistically-selected lakes in the Adirondack region of New York. Calibration of the direct distribution model is based on a step-function application of acid deposition to MAGIC. Comparative evaluations of the resulting model predictions are made using historic deposition estimates and two alternative future deposition scenarios. The predictions of the direct distribution model match well the shapes and patterns of change of the regional distributions of ANC and pH predicted by MAGIC, the short- and medium-term dynamics of these changes, and the effect of including organic acids. However, small, long-term decreases in the fraction of incoming acid deposition neutralized by lakes and their watersheds predicted by MAGIC are not reproduced.     

Evaluation of the effects of acid precipitation in eastern Canada using the raison system

Evaluations have been made of the key chemical factors in the aquatic effects upon surface waters due to acidic precipitation in eastern Canada. The region of Canada east of the Manitoba/Ontario border was divided into 22 aggregates and assessments of inorganic and organic ion chemistry appraised relative to sulphate deposition rates and distributions. Aquatic sensitivity is largely dominated by the concentration, distribution and magnitude of SO _inf4 ^sup2- (sulphate) deposition and by the prevalent geology and derived soils found in each aggregate. The RAISON system provided an adaptable and highly flexible platform to evaluate interactively, multiple data sets of divergent characteristics. Attributes usually associated with geographical information systems are significantly augmented by quantitative numerical and stochastic capabilities that were used extensively in this study.     

Linking groundwaters of high CO2 to aluminium levels in rivers: the case for the upper Severn in mid-Wales

Al is a critical ecotoxicant in surface waters impacted by acidic deposition. Apart from the most acidic surface waters, Al concentrations are often considered to be controlled by Al(OH)(3) or aluminosilicate (clay) solubility for modelling studies. For many UK rivers there is no clear evidence for such solubility controls even though there is the potential under moderately acidic/alkaline conditions. Here, Al solubility in ground and river water is compared for acid sensitive catchments in mid-Wales. The results reveal that there may be a solubility control within the groundwater but a more complex state of affairs within the river. The groundwater is of high CO(2) content and once in the river it degasses to raise pH. However, there is limited change in Al concentration and hence the solubility relationship is lost. The results flag the potential importance of groundwater solubility controls for Al and the potential for the groundwater zone to act as an Al filter. For positive alkalinity groundwaters, the high CO(2) levels depress the pH to near the value for minimum Al solubility. However, there is no simple groundwater end-member. Examining Al solubility controls solely within the rivers provides cryptic and misleading clues to the hydrogeological controls for Al within catchments. Assessing the within-catchment processes requires direct measurement with full consideration of both inorganic and organic attenuation.     

Aluminium concentrations in Swedish forest streams and co-variations with catchment characteristics

The negative effects of elevated concentrations of inorganic aluminium on aquatic organisms are well documented. Acid deposition is often cited as a main driver behind the mobilisation and speciation of aluminium in soils and surface waters. In the study, we tested the hypothesis that sulphur deposition is the main driver for elevated concentrations of inorganic aluminium in 114 base poor, boreal Swedish streams. However, the deposition of anthropogenic sulphate has decreased substantially since it peaked in the 1970s, and at the current deposition levels, we hypothesise that local site parameters play an important role in determining vulnerability to elevated concentrations of inorganic aluminium in boreal stream waters. Presented here are the results of a principal components analysis of stream water chemistry, acid deposition data and local site variables, including forest composition and stem volume. It is shown that the concentrations of both organic and inorganic aluminium are not explained by either historical or current acid deposition, but are instead explained by a combination of local site characteristics. Sites with elevated concentrations of inorganic aluminium were characterised by small catchments (<500 ha) dominated by mature stands of Norway spruce with high stem volume. Using data from the Swedish National Forest Inventory the area of productive forest land in Sweden with a higher vulnerability for elevated inorganic aluminium concentrations in forests streams is approximately 1.5 million hectares or 7% of the total productive forest area; this is higher in the south of Sweden (10%) and lower in the north (2%). A better understanding of the effects of natural processes and forest management in controlling aquatic inorganic aluminium concentrations is therefore important in future discussions about measures against surface water acidification.     

Storm water contamination and its effect on the quality of urban surface waters

We studied the effect of storm water drained by the sewerage system and discharged into a river and a small reservoir, on the example of five catchments located within the boundaries of the city of Poznań (Poland). These catchments differed both in terms of their surface area and land use (single- and multi-family housing, industrial areas). The aim of the analyses was to explain to what extent pollutants found in storm water runoff from the studied catchments affected the quality of surface waters and whether it threatened the aquatic organisms. Only some of the 14 studied variables and 22 chemical elements were important for the water quality of the river, i.e., pH, TSS, rain intensity, temperature, conductivity, dissolved oxygen, organic matter content, Al, Cu, Pb, Zn, Fe, Cd, Ni, Se, and Tl. The most serious threat to biota in the receiver came from the copper contamination of storm water runoff. Of all samples below the sewerage outflow, 74 % exceeded the mean acute value for Daphnia species. Some of them exceeded safe concentrations for other aquatic organisms. Only the outlet from the industrial area with the highest impervious surface had a substantial influence on the water quality of the river. A reservoir situated in the river course had an important influence on the elimination of storm water pollution, despite the very short residence time of its water.     

Thermotolerant coliform loadings to coastal areas of Santa Catarina (Brazil) evidence the effect of growing urbanisation and insufficient provision of sewerage infrastructure

Thermotolerant coliform (TC) loadings were quantified for 49 catchments draining into the North and South Bays of Santa Catarina (SC, southeastern Brazil), an area known for its tourism and aquaculture. TC loadings were calculated based on flow measurements taken in 26 rivers. TC concentrations ere quantified based on surface water samples collected at 49 catchment outlets in 2012 and 2013. Median TC loads ranged from 3.7 × 10³ to 6.8 × 10⁸ MPN s^?1. TC loadings in the catchments increased in proportion to increases in resident human population, population density and percentage of urbanised area. Catchments with more than 60% of area covered by wastewater collection and treatment systems had higher TC loads per person than catchments with less than 25%. Based on the study catchments, these results indicate that current sewerage infrastructure is ineffective in reducing contamination of faecal origin to surface waters. These findings have important implications for the management of microbiological health hazards in bathing, recreational and shellfish aquaculture waters in the North and South Bays of Santa Catarina Island.     

Dealing with heterogeneous regression slopes in analysis of covariance: new methodology applied to environmental effects monitoring fish survey data

Analysis of covariance (ANCOVA) is a powerful statistical method which incorporates one or more covariates into the analysis to reduce error associated with measurement. ANCOVA (modeling response as a function of fish size) is frequently used to analyze environmental effects monitoring (EEM) fish survey data. In approximately 12% of fish survey data sets taken from cycles 1 to 3 of Environment Canada’s EEM database for pulp and paper mills, the standard assumption of parallel regression slopes is not met. For the first three cycles of the EEM program, these data sets were classified as indicating a mill effect, but for the most part were excluded from subsequent analyses aimed at quantifying the effect. We present two different methods for initially dealing with data sets that exhibit heterogeneous slopes so that they can be analyzed using the parallel slope model. The first method identifies data sets where heterogeneous slopes are forced by a few high-influence observations. The second approach identifies data sets where a model with heterogeneous slopes is statistically, but not practically, significant: with a high coefficient of determination for the parallel slope model. These new methodologies are applied to EEM pulp and paper data sets and about 55% of cases with heterogeneous slopes can be described by a parallel slope model. We also discuss a third method that can be used to describe mill effects when regression slopes remain heterogeneous even after applying the above two methods, enabling comparison with a critical effect size. These new methodologies could benefit the EEM program by enabling more data sets to be incorporated into meta-analyses and be used to make more equitable mill monitoring decisions in the future.     

Step-up multiple regression model to compute Chlorophyll a in the coastal waters off Cochin, southwest coast of India

The interaction effects of abiotic processes in the production of phytoplankton in a coastal marine region off Cochin are evaluated using multiple regression models. The study shows that chlorophyll production is not limited by nutrients, but their physiological regulations (responses to nutrients, pH, temperature and salinity) are mainly responsible for the increased biological production. The model explaining 77% of variability for chlorophyll a production is indicative of preconditioning of the coastal waters. The phytoplankton production is found to be sensitive to the environment, which varies seasonally. Further, the study suggests that supply of organic matter and grazing of zooplankton (not included) would improve the model efficiency. Despite this, the good agreement in the computed and measured chlorophyll a values shows that step-up multiple regression model is a useful tool to understand the influence of environmental variables on the production of phytoplankton in these coastal waters.     

Aluminium in UK rivers: a need for integrated research related to kinetic factors, colloidal transport, carbon and habitat

Dissolved aluminium concentrations ([Al]) in the <0.45 μm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SO(x) in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H(+)] - [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO(2) changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.     

Patterns of Spatial Autocorrelation in Stream Water Chemistry

Geostatistical models are typically based on symmetric straight-line distance, which fails to represent the spatial configuration, connectivity, directionality, and relative position of sites in a stream network. Freshwater ecologists have explored spatial patterns in stream networks using hydrologic distance measures and new geostatistical methodologies have recently been developed that enable directional hydrologic distance measures to be considered. The purpose of this study was to quantify patterns of spatial correlation in stream water chemistry using three distance measures: straight-line distance, symmetric hydrologic distance, and weighted asymmetric hydrologic distance. We used a dataset collected in Maryland, USA to develop both general linear models and geostatistical models (based on the three distance measures) for acid neutralizing capacity, conductivity, pH, nitrate, sulfate, temperature, dissolved oxygen, and dissolved organic carbon. The spatial AICC methodology allowed us to fit the autocorrelation and covariate parameters simultaneously and to select the model with the most support in the data. We used the universal kriging algorithm to generate geostatistical model predictions. We found that spatial correlation exists in stream chemistry data at a relatively coarse scale and that geostatistical models consistently improved the accuracy of model predictions. More than one distance measure performed well for most chemical response variables, but straight-line distance appears to be the most suitable distance measure for regional geostatistical modeling. It may be necessary to develop new survey designs that more fully capture spatial correlation at a variety of scales to improve the use of weighted asymmetric hydrologic distance measures in regional geostatistical models.     

Stream ecosystem response to chronic deposition of N and acid at the Bear Brook Watershed, Maine

The Bear Brook Watershed in Maine (BBWM) is a long-term, paired watershed experiment that addresses the effects of acid and nitrogen (N) deposition on whole watersheds. To examine stream response at BBWM, we synthesized data on organic matter dynamics, including leaf breakdown rates, organic matter inputs and standing stocks, macroinvertebrate secondary production, and nutrient uptake in treated and reference streams at the BBWM. While N concentrations in stream water and leaves have increased, the input, standing stocks, and breakdown rates of leaves, as well as macroinvertebrate production, were not responsive to acid and N deposition. Both chronic and acute increases of N availability have saturated uptake of nitrate in the streams. Recent experimental increases in phosphorus (P) availability enhanced stream capacity to take up nitrate and altered the character of N saturation. These results show how the interactive effects of multiple factors, including environmental flow regime, acidification, and P availability, may constrain stream response to chronic N deposition.     

Assessing Potential for Recovery of Biotic Richness and Indicator Species due to Changes in Acidic Deposition and Lake ph in Five Areas of Southeastern Canada

Biological damage to sensitive aquatic ecosystems is among the most recognisable, deleterious effects of acidic deposition. We compiled a large spatial database of over 2000 waterbodies across southeastern Canada from various federal, provincial and academic sources. Data for zooplankton, fish, macroinvertebrate (benthos) and loon species richness and occurrence were used to construct statistical models for lakes with varying pH, dissolved organic carbon content and lake size. pH changes, as described and predicted using the Integrated Assessment Model (Lam et al., 1998; Jeffries et al., 2000), were based on the range of emission reductions set forth in the Canada/US Air Quality Agreement (AQA). The scenarios tested include 1983, 1990, 1994 and 2010 sulphate deposition levels. Biotic models were developed for five regions in southeastern Canada (Algoma, Muskoka, and Sudbury, Ontario, southcentral Québec, and Kejimkujik, Nova Scotia) using regression tree, multiple linear regression and logistic regression analyses to make predictions about recovery after emission reductions. The analyses produced different indicator species in different regions, although some species showed consistent trends across regions. Generally, the greatest predicted recovery occurred during the final phase of emission reductions between 1994 and 2010 across all taxonomic groups and regions. The Ontario regions, on average, were predicted to recover to a greater extent than either southcentral Québec or the Kejimkujik area of Nova Scotia. Our results reconfirm that pH 5.5–6.0 is an important threshold below which damage to aquatic biota will remain a major local and regional environmental problem. This damage to biodiversity across trophic levels will persist well into the future if no further reductions in sulphate deposition are implemented.     

Acid precipitation-related chemical trends in 18 rivers of atlantic Canada — 1983 to 1992

Using non-parametric techniques, we studied water chemistry changes from 1983 to 1992 in 18 rivers located at the extreme northeastern portion of North America. This period was marked by a decrease in sulfate (SO ₄ ^– ) production in eastern Canada from 1982 to 1986, followed by a levelling off from 1986 to 1992. Nitrate (NO ₃ ^– ) production and deposition generally increased over this whole period. We used two time windows, 1983 to 1989 and 1983 to 1992, to determine if changes in river acidification variables occurred over the ten year period. We found significant trends of increasing pH and acid neutralization capacity (ANC) concentrations at eight sites using both time windows, while SO ₄ ^–2 increased at five and seven sites during the same two time periods. Nitrate concentrations showed few consistent trends, while base cations showed increases in the earlier part of the data set and total organic carbon (TOC) showed long-term decreases. There were few significant trends in hydrogen (H⁺), and a slight decrease in SO ₄ ^–2 exports as opposed to increased concentrations over the same period. We attribute the discrepancy between SO ₄ ^–2 concentration and export trends to be due to evapotranspiration in the basins, causing a concentration of ions in water. Nitrate and calcium exports showed no trends, while TOC decreased at four or five sites, depending on the time window used. Longer data sets tended to produce more detectable trends. Overall, water chemistry in the region is showing the effects of reduced SO ₄ ^– loads and is not yet being affected by the increases in NO ₃ ^– deposition.     

Chemistry of Dissolved Organic Carbon at Bear Brook Watershed, Maine: Stream Water Response to (NH4)2SO4 Additions

This study was conducted to determine the response of stream water DOC and organic acidity to increased inputs of ammonium sulfate to a whole catchment. Precipitation, throughfall, soil solutions (from Spodosols) and stream waters were characterized for DOC concentrations and fractions (hydrophobic acids and neutrals, hydrophilic acids, bases, and neutrals) in both the control (East Bear) and the treatment (West Bear) catchments of Bear Brook Watershed, Maine (BBWM), a northern hardwood forest. In all solutions except precipitation, DOC was composed primarily of organic acids, with hydrophobic acids dominating (> 60% of DOC) in forest floor leachates (5000 mol C L-1), and a balance of hydrophobic and hydrophilic acids in deep B horizons and stream waters ( 150 mol C L-1). Stream waters had higher concentrations of DOC during storm or snowmelt events (high discharge), often reaching 300 to 400 mol C L-1. Forest floor leachate C was rapidly attenuated by the mineral soils under all flow conditions, indicating how important mineral soil sorption of DOC was in reducing the loss of C via surface water from BBWM. No differences occurred between control and treatment streams for concentration or composition of DOC due to treatment from 1989 through 1994. In 1995, West Bear Brook had much lower concentrations of DOC than East Bear for the first time. However, this occurred during a year of record low runoff, suggesting that hydrology may have affected export of C. Average annual export of DOC from the catchments was similar (1000 to 2000 mol C ha-1 yr-1). Organic anions in streamwaters increased slightly during high flow events (e.g., East Bear had means of 15 and 19 eq L-1 organic anions during base flow and high discharge in 1995). Treatment of West Bear caused a decrease in organic anions, both in concentration and contribution to overall anion composition (organic anions during high discharge as a percentage of total anions decreased from about 8 to 4% for 1987-89 and 1993-95 samples, respectively). This was probably due to decreased solution pH (greater protonation of organics) and higher concentrations of inorganic anions. Overall, there were no clear, detectable changes in stream water DOC, with only minor changes in organic anions, as a result of treatment with ammonium sulfate.     

Drivers and evolution of episodic acidification at the Bear Brook Watershed in Maine, USA

Despite decades of research about episodic acidification in many regions of the world, the understanding of what controls the transient changes in stream water chemistry occurring during rain and snow melt events is still limited. Here, we use 20 years of hydrological and stream chemical data from the paired watershed study at Bear Brook Watershed in Maine (BBWM), USA to improve the understanding of the effects of acid deposition on the causes, drivers, and evolution of episodic acidification. The long-term experimental study at BBWM includes 18 years of chemical treatment of the West Bear Brook (WB) watershed with (NH₄)₂SO₄. East Bear Brook (EB) serves as reference. The treatment started in 1989 following a 2-year pretreatment period. We analyzed 212 hydrological episodes using an episode model that can separate and quantify individual drivers of the transient change in acid-neutralizing capacity (ANC) during hydrological events. The results suggest that 18 years of N and S addition have not affected the natural drivers of episodic acidification of base-cation dilution, marine sea salt episodes, or organic acidity during rain and snow melt events. The contribution of SO $_{4}^{2-}$ to the ANC decline in WB has been increasing linearly since the beginning of watershed treatment, while the role of NO $_{3}^{-}$ has remained relatively constant after an initial increase. This is contradictory to many previous shorter-term studies and illustrates the need for a more mechanistic understanding of the causes and drivers of episodic acidification during rain- and snow melt-driven hydrological events.     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

Passive sampling of herbicides combined with effect analysis in algae using a novel high-throughput phytotoxicity assay (Maxi-Imaging-PAM)

We propose to combine a passive sampler for polar organic compounds (POS) with a specific bioassay for phytotoxicity to assess the hazard of herbicidal compounds in surface waters. The POS consisted of an Empore disk coated with styrenedivinylbenzene deployed in a Teflon housing, which has relatively high sampling rates (e.g., approximately 1 L d(-1) for diuron). POS were deployed for 5 days in a small-scale field study in South East Queensland, Australia, in a relatively pristine environment and an urban environment to explore sensitivity towards herbicides and potential influences of non-herbicidal pollutants. Besides chemical analysis of 8 herbicides, a novel bioassay (Maxi-Imaging-PAM, IPAM) was employed to assess the phytotoxic effects of water samples and POS extracts. The IPAM allows rapid assessment of photosynthetic quantum yields of a large number of samples via chlorophyll-fluorescence imaging and the saturation pulse method. Sampling rates for several herbicides from laboratory calibrations were found to be applicable under field conditions. Toxic equivalent concentrations (with reference to the herbicide diuron) were computed from the concentrations determined by chemical analysis and the relative potency (also termed toxic equivalence factor) of the detected herbicides. There was good agreement between diuron equivalent concentrations from chemical analysis and diuron equivalent concentrations determined with the IPAM.     

Small-scale temporal variation and the effect of urbanisation on extracellular enzyme activity in streams

The activity of six extracellular enzymes involved in the degradation of dissolved organic carbon compounds was measured in two highly urbanised and two minimally impacted streams east of Melbourne, Australia, using 4-methylumbelliferyl-substrates. Small-scale temporal variation in enzyme activity was determined by repeatedly sampling the same point in the water column, while the effect of flow was determined by sampling in regions of higher and lower flow in both stream types. Replicate samples showed that enzyme activity was not significantly different over small (minutes) time scales. On five of six sampling occasions the enzyme activity was unaffected by flow. On one sampling occasion in a minimally disturbed stream, the difference between the high- and low-flow regions was statistically significant (ANOSIM, Global R= 0.78, P= 0.03). Enzyme activity profiles (activities of the suite of enzymes) of the streams in urbanised catchments were different to those in minimally disturbed catchments. The measurements made in four different streams showed high reproducibility over short time periods (minutes) which lends greater credibility to analogous spatial studies. Although these results determined that small-scale temporal variability was not significant, and that the effects of flow were generally minimal, it is recommended that spatial and temporal variability in the stream be at least considered before any studies measuring extracellular enzyme activity in stream waters are carried out. Such an approach will lead to conclusions from measurements that are not likely to be confounded by variables such as flow rate or time.     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

Consequences and Correctives Related to Lake Acidification, Liming and Mercury in Fish – A Case-Study for Lake Huljesjön, Sweden, Using the LakeWeb-model

This work exemplifies how a given lake (Lake Huljesjön, Sweden) would likely respond to changes in pH-values and to liming (a standard measure against anthropogenic acidification). The basic questions are: How would a liming influence pH? How long would the changes last? How would the changes influence the structure and function of lake ecosystems? The work uses a comprehensive lake ecosystem model, LakeWeb, which accounts for production, biomasses, predation, abiotic/biotic interactions of nine key functional groups of organisms, phytoplankton, bacterioplankton, two types of zooplankton (herbivorous and predatory), two types of fish (prey and predatory), zoobenthos, macrophytes and benthic algae. LakeWeb is a dynamic model and gives weekly variations. It has been critically tested using empirical data and regressions from many lakes. Those tests are not presented here but have shown that the model can capture typical functional and structural patterns in lakes very well. This gives credibility to the results presented in this work, which would be very costly to obtain in the traditional manner by extensive field studies in one or a few lakes. This work presents for the first time predictions at the ecosystem level of how functional groups of organisms (and not individual species) are likely to respond to acidification and liming. Two existing dynamic models, one for liming, the other for Hg-concentrations in fish, have been added to the LakeWeb-model. These two models have previously been tested and proven to yield good predictions. The results presented here indicate that there are several probable changes in the structure and function of the lake foodweb related to acidification and liming. The predicted changes in macrophyte cover will influence the predation pressure on fish, and thereby the fish biomass. Reductions in primary production at low pH-values will cause reductions in fish biomass. There are several interesting compensatory effects between factors that increase fish biomass and factors that tend to decrease the biomass. Such matters can be handled quantitatively by the LakeWeb-model.