The MAGIC simulation of surface water acidification at, and first year results from, the Bear Brook Watershed Manipulation, Maine, USA

The catchments of East and West Bear Brooks, Maine, USA, have been hydrologically and chemically monitored for 3.5 years. Stream chemistries and hydrographs are similar. These clear water streams are low in ANC (0-70 microeq litre(-1)), with variations caused by changing concentrations of base cations, SO4, NO3 and Cl. The latter range between 90-120, 0-40 and 65-75 microeq litre(-1), respectively. The West Bear catchment is being treated with six applications per year of dry (NH4)2SO4 at 1800 eq ha(-1) year(-1). After one year of treatment, the response of the stream chemistry and the response modelled by MAGIC are similar. Retentions of NH4 and SO4 are nearly 100% and greater than 80%, respectively. The additional flux of SO4 is compensated principally by an increased Ca concentration. Episodes of high discharge in the treated catchment are now characterized by lower ANC and pH, and higher Al than prior to the manipulation. Concentrations of NO3 have increased about 10 microeq litre(-1) during the dormant season, presumably due to additional nitrification of N from NH4. Discharge-chemistry relationships indicate that changes in stream chemistry, except for NO3, are dominated by ion exchange reactions in the upper part of the soil profile.     

Recovery from acidification in central Europe--observed and predicted changes of soil and streamwater chemistry in the Lysina catchment,Czech Republic

The geochemical model MAGIC was applied to estimate streamwater and soil chemistry between 1851 and 2030 at the Lysina catchment, an acid-sensitive granitic catchment covered by planted Norway spruce monoculture in the western Czech Republic. The total deposition of sulfur to the catchment was 164 meq m(-2) in 1991, but had declined to 52 meq m(-2) by 2000. Although SO2 emissions in the region declined by 90% compared to the 1980s, acidification recovery was small within the period 1990-2000. Stream pH increased only slightly (from 3.92 to 4.07), although SO4 concentration declined sharply from 568 microeq l(-1) (1990) to 232 microeq l(-1) (2000). Organic acids played an important role in streamwater buffering. According to the MAGIC prediction using deposition measured in 1999-2000, streamwater pH will increase to 4.3 and soil base saturation will increase to 6.2% by 2030 (from 5.7% in 2002). Pre-industrial pH was estimated to be 5.5 and soil base saturation 24.7%. The loss of base cations (Ca, Mg, Na, K) was caused predominantly by atmospheric acidity, but intensive forestry was responsible for approximately one third of the net base cation loss via accumulation in harvested biomass. Severely damaged sites, under continued pressure from forestry, will not return to a good environmental status in the near future (if ever) when the acid deposition input is only partially reduced.     

An experimental ecotoxicological study and its application to the behavioural study of organic mercury (CH3HgCl) in the environment: influence of temperature and pH

Laboratory experiments were carried out to study the influence of temperature (24, 28 and 30 °C) and pH (1–10) on organic mercury (CH₃HgCl) transfer and accumulation in an experimental ecotoxicological model. We followed the evolution of CH₃HgCl in a basic model (water+air) by varying temperature and pH. In a second step, we completed the model by adding sediment and fish. We added CH₃HgCl to water at the beginning of each experiment which was repeated at least three times. Results demonstrated that mercury was released from methylmercury into the air regardless of water pH and its concentration in the air increased with increasing pH. By contrast, in presence of sediment, almost all the mercury was fixed onto the sediment and no mercury was traced in air or in water. Interestingly, in the presence of sediment, the life span of fish under methylmercury exposure lasted longer despite their higher mercury body level content at their death. These results indicate that water is a bad exposure indicator for aquatic pollution. In case of chronic pollution, sediments, fish and aquatic plants are more appropriate indicators.     

An experimental ecotoxicological study and its application to the behavioural study of organic mercury (CH3HgCl) in the environment: influence of temperature and pH

Laboratory experiments were carried out to study the influence of temperature (24, 28 and 30 °C) and pH (1–10) on organic mercury (CH₃HgCl) transfer and accumulation in an experimental ecotoxicological model. We followed the evolution of CH₃HgCl in a basic model (water+air) by varying temperature and pH. In a second step, we completed the model by adding sediment and fish. We added CH₃HgCl to water at the beginning of each experiment which was repeated at least three times. Results demonstrated that mercury was released from methylmercury into the air regardless of water pH and its concentration in the air increased with increasing pH. By contrast, in presence of sediment, almost all the mercury was fixed onto the sediment and no mercury was traced in air or in water. Interestingly, in the presence of sediment, the life span of fish under methylmercury exposure lasted longer despite their higher mercury body level content at their death. These results indicate that water is a bad exposure indicator for aquatic pollution. In case of chronic pollution, sediments, fish and aquatic plants are more appropriate indicators.     

Mineralogical study and leaching behavior of a stabilized harbor sediment with hydraulic binder

The environmental assessment of potential effects of contaminated harbor sediments stabilized with hydraulic binders and the determination of remediation endpoints require the determination of pollutants leaching potentials. Moreover, little information about the speciation and mobility of inorganic contaminants in these specific solid matrices is available in the literature. The objective of this paper is to investigate the relationship between mineralogy and leachability of contaminants (copper, lead, and zinc) present in a French harbor sediment stabilized with quicklime and Portland cement. Batch equilibrium leaching tests at various pH, chemical analysis of leachates, and mineralogical studies (X-ray diffraction, scanning electron microscopy–energy dispersive spectroscopy, and diffuse reflectance infrared Fourier transform) have been combined in the present investigation. The acid neutralization capacity of the stabilized matrix studied is first controlled by the dissolution of portlandite (pH?~12), followed by the dissolution of C–S–H (pH?~11) and the dissolution of ettringite (pH?~10). Finally, a very high buffering capacity of this stabilized sediment is observed for pH values around 6. This equilibrium is mainly controlled by the dissolution of iron sulfides and carbonate minerals. Consequently, the mobilization of inorganic contaminants as a function of pH remains very low (<0.1 wt%) for pH values above 6 and significantly increases for pH below these values. This research confirms the importance of a combined methodology for the intrinsic characterization of potential mobilization of contaminants in a stabilized sediment and for a better understanding of geochemical processes that affect contaminant fate, transformation, and transport in the subsurface environment.     

The effect of manipulating sediment pH on the porewater chemistry of copper- and zinc-spiked sediments

Spiking of sediment with metal cations that readily hydrolyse causes the sediment pH to decrease. Displaced iron and manganese also oxidise and hydrolyse, further lowering sediment pH. The lower pH of metal-spiked sediments requires a subsequent sediment neutralisation. This research compared the pH adjustment of Cu- and Zn-spiked sediments using single and multiple additions of 1M NaOH. Sediment pH, redox potential, and porewater metal concentrations were monitored over 40 days. Depth profiles were also measured to investigate stratification. A single pH adjustment to pH 7 and 8 initially counteracted the pH change caused by metal additions, however, pH continued to decrease slowly thereafter. Multiple pH adjustments diminished porewater Cu, Zn and Fe concentrations to a greater extent than a single pH adjustment, but the ongoing oxidative precipitation of porewater metals continued to consume OH(-) ions and impede pH maintenance. Displacement of high iron(II) concentrations and the opposing rates of iron(II) oxidative precipitation and bacterially-mediated iron(II) production, affected the partitioning of the added metals between the sediment and pore water. Despite similar pH over the spiked-metal concentration gradient following pH adjustment, sediments spiked with higher metal concentrations produced lower porewater Fe concentrations, possibly due to toxicity to iron(III) oxyhydroxide reducing bacteria. Distinct stratification of redox potential and dissolved Fe and Cu developed over a depth of 6cm during the 40-day equilibration period. Recommendations are provided on methods for preparing metal-spiked sediments in which the partitioning of metals between dissolved and particulate phases better resembles that of in situ (field) metal-contaminated sediments.     

扬水曝气器的水质改善功能及提水、充氧性能研究

扬水曝气器是水源水质改善设备,应用于湖泊水库水源地,抑制藻类生长,控制底泥污染物释放,取得了良好的效果.建立了扬水曝气器上升流速数学模型,用于模拟计算扬水曝气器的提水能力.建立了扬水曝气器曝气室的充氧能力数学模型.在实验室实测了扬水曝气器上升流速及其对水体的充氧过程,实测值与模拟计算值吻合较好,验证了提水、充氧能力数学模型.     

Sorption of thallium(I) onto geological materials: influence of pH and humic matter

The sorption behaviour of the severely toxic heavy metal thallium (Tl) as a monovalent cation onto three representative materials (goethite, pyrolusite and a natural sediment sampled from a field site) was examined as a function of pH in the absence and presence of two natural humic acids (HAs), using ²⁰⁴Tl(I) as a radiotracer. In order to obtain a basic understanding of trends in the pH dependence of Tl(I) sorption with and without HA, sorption of HAs and humate complexation of Tl(I) as a function of pH were investigated as well. In spite of the low complexation between Tl(I) and HAs, the presence of HAs results in obvious alterations of Tl(I) sorption onto pyrolusite and sediment. An influence on Tl(I) sorption onto goethite was not observed. Predictions of K_d (distribution coefficient) for Tl(I) on goethite in the presence of HAs, based on a linear additive model, agree well with the experimental data, while a notable disagreement occurs for the pyrolusite and sediment systems. Accordingly, it is suggested that HAs and goethite may act as a non-interacting sorbent mixture under the given conditions, but more complex interactions may take place between the HAs and the mineral phases of pyrolusite or sediment.     

Uncertainty Analysis of Hydrologic and Water Quality Predictions for a Small Watershed Using SWAT2000

Hydrologic and water quality (H/WQ) models are being used with increasing frequency to devise alternative pollution control strategies. It has been recognized that such models may have a large degree of uncertainty associated with their predictions, and that this uncertainty can significantly impact the utility of the model. In this study, ARRAMIS (Advanced Risk & Reliability Assessment Model) software package was used to analyze the uncertainty of the SWAT2000 (Soil and Water Assessment Tool) outputs concerning nutrients and sediment losses from agricultural lands. ARRAMIS applies Monte Carlo simulation technique connected with Latin hypercube sampling (LHS) scheme. This technique is applied to the Warner Creek watershed located in the Piedmont physiographic region of Maryland, and it provides an interval estimate of a range of values with an associated probability instead of a point estimate of a particular pollutant constituent. Uncertainty of model outputs was investigated using LHS scheme with restricted pairing for the model input sampling. Probability distribution functions (pdfs) for each of the 50 model simulations were constructed from these results. Model output distributions of interest in this analysis were stream flow, sediment, organic nitrogen (organic-N), organic phosphorus (organic-P), nitrate, ammonium, and mineral phosphorus (mineral-P) transported with water. Developed probability distribution functions for the model provided information with desirable probability. Results indicate that consideration of input parameter uncertainty produces 64% less mean stream flow along with approximately 8.2% larger sediment loading than obtained using mean input parameters. On the contrary, mean of outputs regarding nutrients such as nitrate, ammonia, organic-N, and organic-P (but not mineral-P) were almost the same as the one using mean input parameters. The uncertainty in predicted stream flow and sediment loading is large, but that for nutrient loadings is the same as that of the corresponding input parameters. This study concluded that using a best possible distribution for the input parameters to reflect the impact of soils and land use diversity in a small watershed on SWAT2000 model outputs may be more accurate than using average values for each input parameter.     

Modelling assessment of regional groundwater contamination due to historic smelter emissions of heavy metals

Historic emissions from ore smelters typically cause regional soil contamination. We developed a modelling approach to assess the impact of such contamination on groundwater and surface water load, coupling unsaturated zone leaching modelling with 3D groundwater transport modelling. Both historic and predictive modelling were performed, using a mass balance approach for three different catchments in the vicinity of three smelters. The catchments differ in their hydrology and geochemistry. The historic modelling results indicate that leaching to groundwater is spatially very heterogeneous due to variation in soil characteristics, in particular soil pH. In the saturated zone, cadmium is becoming strongly retarded due to strong sorption at neutral pH, even though the reactivity of the sandy sediments is low. A comparison between two datasets (from 1990 to 2002) on shallow groundwater and modelled concentrations provided a useful verification on the level of statistics of "homogeneous areas" (areas with comparable land use, soil type and geohydrological situation) instead of comparison at individual locations. While at individual locations observations and the model varies up to two orders of magnitude, for homogeneous areas, medians and ranges of measured concentrations and the model results are similar. A sensitivity analysis on metal input loads, groundwater composition and sediment geochemistry reveals that the best available information scenario based on the median value of input parameters for the model predicts the range in observed concentrations very well. However, the model results are sensitive to the sediment contents of the reactive components (organic matter, clay minerals and iron oxides). Uncertainty in metal input loads and groundwater chemistry are of lesser importance. Predictive modelling reveals a remarkable difference in geochemical and hydrological controls on subsurface metal transport at catchment-scale. Whether the surface water load will peak within a few decades or continue to increase until after 2050 depends on the dominant land use functions in the areas, their hydrology and geochemical build-up.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH(-) . pH(-1). The sediments were spiked with atrazine at 7.25-36.23 mg kg(-1) (6.21 x 10(-7)-3.09 x 10(-6) mol atrazine . g(-1) sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 x 10(-2)-7.04 x 10(-2) d(-1) for the atrazine-spiked sediments.     

A comparison of nonlinear regression and neural network models for ground-level ozone forecasting

A hybrid nonlinear regression (NLR) model and a neural network (NN) model, each designed to forecast next-day maximum 1-hr average ground-level O3 concentrations in Louisville, KY, were compared for two O3 seasons--1998 and 1999. The model predictions were compared for the forecast mode, using forecasted meteorological data as input, and for the hindcast mode, using observed meteorological data as input. The two models performed nearly the same in the forecast mode. For the two seasons combined, the mean absolute forecast error was 12.5 ppb for the NLR model and 12.3 ppb for the NN model. The detection rate of 120 ppb threshold exceedances was 42% for each model in the forecast mode. In the hindcast mode, the NLR model performed marginally better than the NN model. The mean absolute hindcast error was 11.1 ppb for the NLR model and 12.9 ppb for the NN model. The hindcast detection rate was 92% for the NLR model and 75% for the NN model.     

Acidification, metals and macrophytes

Plant-specific and metal-specific uptake of Al, Cd, Pb and Hg are reviewed, using examples from bryophytes, lichens, wetland plants, woody plants and crop plants. Ranges of plant metal concentration, toxic thresholds and effects, and effects of metal on biomass are derived from the literature. Relationships of metal in plants to metals in sediment, soil water and air are discussed. Plant Al is negatively correlated with pH of water in lakes and with soil pH. Cadmium in crop plants is negatively related to soil pH. Lead in submergents is related negatively to sediment pH at 4.5 to 6. Little information on plant Hg was available. Factors affecting plant uptake include soil or sediment organic content, carbon exchange capacity, oxide and carbonate content, and Eh as well as total metal content.     

Long-term copper partitioning of metal-spiked sediments used in outdoor mesocosms

Understanding the effects of sediment contaminants is pivotal to reducing their impact in aquatic environments. Outdoor mesocosms enable us to decipher the effects of these contaminants in environmentally realistic scenarios, providing a valuable link between laboratory and field experiments. However, because of their scale, mesocosm experiments are often complex to set up and manage. The creation of environmentally realistic conditions, particularly when using artificially contaminated sediment, is one issue. Here, we describe changes in geochemistry over 1.5 years of a sediment spiked with four different concentrations of copper, within a large freshwater mesocosm facility. The spiking procedure included proportional amendments with garden lime to counteract the decreases in pH caused by the copper additions. The majority of copper within the spiked mesocosm sediments partitioned to the particulate phase with low microgram per liter concentrations measured in the pore waters and overlying waters. The minimum partition coefficient following equilibration between pore waters and sediments was 1.5?×?10⁴ L/kg, which is well within the range observed for field-contaminated sediments (1?×?10⁴ to 1?×?10⁶ L/kg). Recommendations are made for the in situ spiking of sediments with metals in large outdoor mesocosms. These include selecting an appropriate sediment type, adjusting the pH, allowing sufficient equilibration time, and regular mixing and monitoring of metal partitioning throughout the experimental period.     

Use of historical assessment for evaluation of process-based model projections of future environmental change: Lake acidification in the Adirondack mountains, New York, USA

Because of the considerable uncertainties associated with modeling complex ecosystem processes, it is essential that every effort be made to test model performance prior to relying on model projections for assessment of future surface water chemical response to environmental perturbation. Unfortunately, long-term chemical data with which to validate model performance are seldom available. The authors present here an evaluation of historical acidification of lake waters in the northeastern United States, and compare historical changes in a set of lakes to hindcasts from the same watershed model (MAGIC) used to estimate future changes in response to acidic deposition. The historical analyses and comparisons with MAGIC model hindcasts and forecasts of acid-base response demonstrate that the acidic and low-ANC lakes in this region are responsive to strong acid inputs. However, the model estimates suggest lakewater chemistry is more responsive to atmospheric inputs of sulfur than do the estimates based on paleolimnological historical analyses. A 'weight-of-evidence approach' that incorporates all available sources of information regarding acid-base response provides a more reasonable estimate of future change than an approach based on model projections alone. The results of these analyses have important implications for predicting future surface water chemical change in response to acidic deposition, establishing critical loads of atmospheric pollutants, and other environmental assessment activities where natural variation often exceeds the trends under investigation (high noise-to-signal ratio). Under these conditions, it is particularly important to evaluate future model projections in light of historical trends data.     

A review on the application of microbial toxicity tests for deriving sediment quality guidelines

The results of microbial toxicity tests are needed for the risk assessment of polluted sediments. In comparison with animals the anaerobic microorganisms are more tolerant to natural sediment conditions whereas they are more sensitive for a number of specific pollutants. Microbial toxicity tests from a literature search were classified in seven categories. Category A, B and C use polluted sediments and are applied for sediment monitoring. In category D, a pure chemical is added and the organisms and the test conditions were derived from sediment. Therefore this category can be used for setting sediment quality guidelines which protect sediment functions for the toxic effects of chemicals. In category E, organisms from a polluted site are separated from the sediment and are tested with pure chemicals. Organisms from a more polluted site can be more tolerant to a local pollutant. This is called pollution-induced community tolerance and can be used as evidence for the occurrence of toxic effects in a specific sediment. In category F pure chemicals are tested with a pure culture of microorganisms under sediment conditions. The results of category F tests can be combined with single species tests with animals and plants to obtain sediment quality guidelines sufficient for species protection. This can be compared with the sediment quality guidelines which protect sediment functions. When one of these quality guidelines is exceeded for a compound at a specific location a category E test can be used to determine whether the compound shows toxic effects in that sediment.     

pH值对霞湾港沉积物重金属Zn、Cu释放的影响

以霞湾港(铜霞路段)的底泥沉积物为研究对象,采用重金属连续浸提法对重金属Zn、Cu在沉积物中的5种形态进行浸提,分析了其分布特征和在不同pH值与时间的条件下重金属的释放规律。研究结果表明,重金属Zn主要以铁锰氧化物结合态和碳酸盐结合态的形态存在,Cu主要以有机结合态和残渣态的形态存在,可交换离子态的重金属含量都很低。重金属Zn、Cu从沉积物中的释放,主要是在酸性条件下发生,在酸性区内释放量随pH的升高而迅速降低。释放能力和释放速率均为ZnCu,它们释放的过程基本相似,释放速率都比较小,向环境中的释放是个长期过程。     

杀虫剂十氯酮的多介质环境行为模拟

应用EQC模型模拟十氯酮在多介质环境中的归宿和迁移通量.结果表明:土壤是十氯酮最大的贮存库,在稳态平衡条件下,残留率达到95.0%;在稳态非平衡条件下,十氯酮单独排放到水体,有37.5%残留在于排放的水体中,其在大气的浓度水平和质量分布均很低,在沉积物中的质量则来自于水体向沉积物的沉降迁移;十氯酮主要通过水体的水平迁移和土壤的厌氧降解输出;十氯酮的主要界面迁移过程是大气向土壤的迁移,其次是水体向沉积物的沉降和大气向水体的迁移.     

Development and application of a sediment toxicity test using the benthic cladoceran Chydorus sphaericus

This study reports on the development and application of a whole sediment toxicity test using a benthic cladoceran Chydorus sphaericus, as an alternative for the use of pelagic daphnids. A C. sphaericus laboratory culture was started and its performance under control conditions was optimised. The test was firstly validated by determining dose-response relationships for aqueous cadmium and copper and ammonia, showing a sensitivity of C. sphaericus (96 h LC(50) values of 594 microg Cd/L, 191 microg Cu/L and 46 mg ammonia/L at pH 8) similar to that of daphnids. Next, sediment was introduced into the test system and a series of contaminated sediments from polluted locations were tested. A significant negative correlation between survival and toxicant concentrations was observed. It is concluded that the test developed in the present study using the benthic cladoceran C. sphaericus is suitable for routine laboratory sediment toxicity testing.     

Historical trends of polychlorinated dibenzo-p-dioxins and dibenzofurans in three dated sediment cores from Mexico

This paper describes the first report of dioxins and furans (PCDDs/Fs) in sediment cores from Mexico. Sedimentation rates and vertical fluxes were estimated using ²¹⁰Pb dating. Two cores correspond to marine sediments and one to an endorheic lake. Concentrations of PCDDs/Fs found in the three sites are typical of non-impacted areas with low concentrations when compared to reference values. However the PCDDs/Fs sediment profiles show an increasing concentration trend in the upper core sections. This behavior is different from that found at many sites around the globe where diminishing concentrations have been reported. A strong predominance of OCDD was observed, and a comparison to typical composition profiles of industrial and other sources did not result in clear origin assignments for these measured compounds. We suggest that local sources may be responsible for the increase in concentration and, because these undetermined sources have not been curtailed, their importance is still growing.