Field calibration of surface: A model of agricultural chemicals in surface waters

Abstract

Agricultural chemicals sporadically occur at detectable levels in the surface waters of intensively farmed watersheds. HSPF, a previously released model of agricultural chemicals in surface water, had been used to predict concentrations which were much higher (10 X) than those actually observed during monitoring studies. A new model, SURFACE, is described here which is much simpler than HSPF and gives better predictions of surface water concentrations. SURFACE uses PRZM, an EPA model, to calculate edge‐of‐field runoff losses and simple hydraulic routing algorithms to determine concentrations at the bottom of large river basins. In water systems sampled during 1985 and 1986, SURFACE predictions of annualized mean concentrations for alachlor, atrazine, cyanazine and metolachlor were within 0.09 ppb half of the time.     

Post-fire surface water quality: comparison of fire retardant versus wildfire-related effects

An understanding of the environmental effects of the use of wildland fire retardant is needed to provide informed decision-making regarding forest management. We compiled data from all post-fire surface water monitoring programs where the fire retardant constituents ammonia, phosphorus, and cyanide were measured, and data were available in the public domain. For streams near four major wildfires, we evaluated whether these chemicals originated primarily from fire or from retardant use. We compared measured concentrations in streams where chemical wildland fire retardant was applied with concentrations in streams draining areas where retardant was not used. Correlations with calcium provided an additional line of evidence, because calcium concentrations in ash are much higher than in retardant. Ammonia, phosphorus, and total cyanide were found in streams in burned areas where retardant was not used, at concentrations similar to those found in areas where retardant was applied. Concentrations of weak acid dissociable cyanide were generally non-detected or very low, whether or not wildland fire retardant was used in the watershed. These results indicate that the application of wildland fire retardant had minimal effects on proximate surface water quality. Cyanide concentrations in post-fire stormwater runoff were not affected by the presence of ferrocyanide in the retardant formulas and were due to pyrogenic sources.     

Persistent organic pollutants in water and surface sediments of Taihu Lake,China and risk assessment

Organic pollutants, especially persistent organic pollutants were examined in the water and surface sediments of Taihu Lake, China. Both 12 water and 12 sediment samples were collected over the lake. C-18 solid-phase extraction technique was applied to extract organic pollutants in collected water samples. Soxhlet extraction procedure was used to extract organic pollutants in sediment samples. The analysis was performed by GC-MS controlled by a Hewlett Packard chemstation. Two hundred and seventy-three kinds of organic chemicals in water were examined, 200 more than that detected in 1985; 188 kinds of chemicals in sediments were detected as well. Among them 21 kinds of chemicals belong to priority pollutants as well as 17 kinds to be the endocrine disruptors. The concentrations of the pollutants were more than 2 times higher than that in 1985. The possible source and relation to anthropogenic activity were discussed.     

Comprehensive study on parameter sensitivity for flow and nutrient modeling in the Hydrological Simulation Program Fortran model

Numerous parameters are used to construct the HSPF (Hydrological Simulation Program Fortran) model, which results in significant difficulty in calibrating the model. Parameter sensitivity analysis is an efficient method to identify important model parameters. Through this method, a model’s calibration process can be simplified on the basis of understanding the model’s structure. This study investigated the sensitivity of the flow and nutrient parameters of HSPF using the DSA (differential sensitivity analysis) method in the Xitiaoxi watershed, China. The results showed that flow was mostly affected by parameters related to groundwater and evapotranspiration, including DEEPFR (fraction of groundwater inflow to deep recharge), LZETP (lower-zone evapotranspiration parameter), and AGWRC (base groundwater recession), and most of the sensitive parameters had negative and nonlinear effects on flow. Additionally, nutrient components were commonly affected by parameters from land processes, including MON-SQOLIM (monthly values limiting storage of water quality in overland flow), MON-ACCUM (monthly values of accumulation), MON-IFLW-CONC (monthly concentration of water quality in interflow), and MON-GRND-CONC (monthly concentration of water quality in active groundwater). Besides, parameters from river systems, KATM20 (unit oxidation rate of total ammonia at 20 °C) had a negative and almost linear effect on ammonia concentration and MALGR (maximal unit algal growth rate for phytoplankton) had a negative and nonlinear effect on ammonia and orthophosphate concentrations. After calibrating these sensitive parameters, our model performed well for simulating flow and nutrient outputs, with R ² and E_NS (Nash–Sutcliffe efficiency) both greater than 0.75 for flow and greater than 0.5 for nutrient components. This study is expected to serve as a valuable complement to the documentation of the HSPF model to help users identify key parameters and provide a reference for performing sensitivity analyses on other models.     

Validation of the surface sink model for sorptive interactions between VOCs and indoor materials

Adsorption and desorption by indoor surface materials can have significant impacts on the level of volatile organic compounds (VOCs) indoors. The surface sink model (SSM) was developed to account for these interactions in an indoor air quality model. Two types of scale-up experiments were conducted to validate the SSM that was developed based on small-scale chamber experiments. Conflicting results were obtained from a large-scale laboratory experiment and a field test. From the large-scale laboratory experiment involving three materials and three chemicals, relatively good agreement was observed between measurements and predictions by the SSM. In contrast, the level of sorption in the field test was observed to be at least 9 times greater than was predicted by the SSM.     

Predicting diffuse-source transfers of surfactants to surface waters using SWAT

Chemicals present in domestic wastewater can adsorb to solid phase materials during sewage treatment. If biosolids (or sewage sludge) are applied to land, these chemicals can be transferred to soil. Under some circumstances they can also be transferred to surface waters during storm events either in solution or attached to sediment. In this paper we describe the utility of the SWAT 2000 model to estimate diffuse-source surface water exposure to "down-the-drain" chemicals. The model was applied hypothetically to predict the behaviour of linear alkylbenzene sulphonate (LAS), an anionic surfactant commonly used in household detergents, in a small catchment in Bedfordshire, UK, where it has previously been successfully validated for stream flow, sediments and pesticides. LAS transfers were estimated for two scenarios: (1) realistic and (2) reasonable worst case, based on assumptions on sludge application rates and the concentration of LAS in sludge. In addition, the sensitivity of the model output to the proportion of the catchment to which sludge is applied was established. Soil wetness and the total quantity of biosolids applied were the biggest determinants of chemical transport from the catchment. The potential of SWAT as a higher-tier tool in environmental risk assessments is discussed.     

Runoff of pesticides from rice fields in the Ile de Camargue (Rhône river delta, France): field study and modeling

A field study on the runoff of pesticides was conducted during the cultivation period in 2004 on a hydraulically isolated rice farm of 120 ha surface with one central water outlet. Four pesticides were studied: Alphamethrin, MCPA, Oxadiazon, and Pretilachlor. Alphamethrin concentrations in runoff never exceeded 0.001 microg L(-1). The three other pesticides were found in concentrations between 5.2 and 28.2 microg L(-1) in the runoff water shortly after the application and decreased thereafter. The data for MCPA compared reasonably well with predictions by an analytical runoff model, accounting for volatilization, degradation, leaching to groundwater, and sorption to soil. The runoff model estimated that runoff accounted for as much as 18-42% of mass loss for MCPA. Less runoff is observed and predicted for Oxadiazon and Pretilachlor. It was concluded that runoff from rice paddies carries important loads of dissolved pesticides to the wetlands in the Ile de Camargue, and that the model can be used to predict this runoff.     

An assessment of the environmental fate and exposure of benzene and the chlorobenzenes in Canada

Systematic modelling of the fate of benzene and the chlorobenzenes is presented which follows a four-stage process of chemical classification, quantifying discharge rates and environmental concentrations, evaluative assessment of fate and regional mass balance modelling has been carried out for the southern Ontario region. The EQC model was applied to determine the principal transport and transformation processes experienced by this group of chemicals, which vary considerably in volatility and hydrophobicity. Observed environmental concentrations are in satisfactory agreement with the predictions of the steady state Level III ChemCAN model of chemical fate. A multiple pathway human exposure model which estimates intake of contaminants by residents of southern Ontario has been developed and applied to these chemicals. A novel method of deducing maximum tolerable environmental concentrations is presented. Results suggest that benzene and 1,4-dichlorobenzene are present in the environment at levels sufficient to cause exposures near allowable daily intake (ADI) levels for the general population, but the other substances are present at levels which result in exposure ranging from 1/10 to 1/1000 of the ADI.     

Calcium chloride and calcium bromide aqueous solutions of technical and analytical grade in Lemna bioassay

Saturated water solutions of calcium chloride, calcium bromide and their 1:1 mixture are commonly used as "high density brines" for pressure control in oil wells. To compare the effect of these chemicals of technical grade with the effect of the chemicals of analytical grade the Lemna test was used. The multiplication rate, fresh weight, dry to fresh weight ratio, area covered by plants and chlorophyll content were measured as toxicity parameters. The concentrations of tested chemicals were 0.025, 0.05. 0.075 and 0.1 mol dm(-3). Generally, the chemicals of both technical and analytical grade in concentrations of 0.025 mol dm(-3) stimulated the Lemna minor growth, while tested chemicals in concentrations of 0.05 mol dm(-3) did not affect the growth significantly. The exceptions were results obtained by measuring fresh weight. Most of tested chemicals in concentrations of 0.075 mol dm(-3) and all chemicals in concentrations of 0.1 mol dm(-3) reduced the growth. No major differences between effects of tested chemicals of technical and analytical grade on plant growth were observed, except that tested chemicals of analytical grade in concentrations of 0.1 mol dm(-3) increased dry to fresh weight ratio much stronger than chemicals of technical grade. All tested chemicals in all concentrations increased chlorophyll content. After treatment with chemicals of analytical grade much higher increase of chlorophyll a concentration in comparison to increase of chlorophyll b was noticed, while chemicals of technical grade caused more prominent increase of chlorophyll b.     

Application of non-linear automatic optimization techniques for calibration of HSPF.

Development of TMDLs (total maximum daily loads) is often facilitated by using the software system BASINS (Better Assessment Science Integrating point and Nonpoint Sources). One of the key elements of BASINS is the watershed model HSPF (Hydrological Simulation Program Fortran) developed by USEPA. Calibration of HSPF is a very tedious and time consuming task, more than 100 parameters are involved in the calibration process. In the current research, three non-linear automatic optimization techniques are applied and compared, as well an efficient way to calibrate HSPF is suggested. Parameter optimization using local and global optimization techniques for the watershed model is discussed. Approaches to automatic calibration of HSPF using the nonlinear parameter estimator PEST (Parameter Estimation Tool) with its Gauss-Marquardt-Levenberg (GML) method, Random multiple Search Method (RSM), and Shuffled Complex Evolution method developed at the University of Arizona (SCE-UA) are presented. Sensitivity analysis was conducted and the most and the least sensitive parameters were identified. It was noted that sensitivity depends on number of adjustable parameters. As more parameters were optimized simultaneously--a wider range of parameter values can maintain the model in the calibrated state. Impact of GML, RSM, and SCE-UA variables on ability to find the global minimum of the objective function (OF) was studied and the best variables are suggested. All three methods proved to be more efficient than manual HSPF calibration. Optimization results obtained by these methods are very similar, although in most cases RSM outperforms GML and SCE-UA outperforms RSM. GML is a very fast method, it can perform as well as SCE-UA when the variables are properly adjusted, initial guess is good and insensitive parameters are eliminated from the optimization process. SCE-UA is very robust and convenient to use. Logical definition of key variables in most cases leads to the global minimum.     

Development of a Dynamic Aquatic Model (DynA Model): Estimating Temporal Emissions of DDT to Lake Maggiore (N. Italy)

- DOI: http://dx.doi.org/10.1065/espr2006.01.009 Background, Aims and Scope Most existing models used to describe the fate of chemicals in surface water and sediment generally consider a 'static scenario', in which a contaminant is discharged at a constant rate and environmental input parameters do not change during the simulation time. This approach is not suitable in environmental scenarios characterized by daily or periodic changes of several input parameters. The aim of this study is to estimate approximate emissions of DDT lo Lake Maggiore using a new surface water model, (DynA Model) that describes the fate of a chemical in a dynamic scenario. Methods The model is developed on the grounds of an existing and validated model (QWASI). A numerical solution was adopted to build the fully dynamic version of the model. Results and Discussion The model was applied to Lake Maggiore emitting DDT at a constant rate until steady-state was reached. Emissions were stopped and later sporadic 'pulse' emissions were added. This was done to calculate the amount of DDT needed to simulate concentrations close to those measured in water and sediments. This allowed the evaluation of the order of magnitude of emissions. An uncertainty analysis for sediment resuspension was also performed, given the lack of measured resuspension rates. Conclusion The model showed the time response of the Lake Maggiore system to varying emission scenarios and provided what are regarded as reasonable estimates of DDT emissions. The model demonstrated the importance of sediment-water exchange. Recommendation and Outlook In order to better calculate DDT concentrations the model should be run with different discharge scenarios to clarify the time trends of concentrations, possibly with the use of different sets of measured data (such as biota and sediment deposition/resuspension rates).     

Classifying environmental pollutants: Part 3. External validation of the classification system

In order to validate a classification system for the prediction of the toxic effect concentrations of organic environmental pollutants to fish, all available fish acute toxicity data were retrieved from the ECETOC database, a database of quality-evaluated aquatic toxicity measurements created and maintained by the European Centre for the Ecotoxicology and Toxicology of Chemicals. The individual chemicals for which these data were available were classified according to the rulebase under consideration and predictions of effect concentrations or ranges of possible effect concentrations were generated. These predictions were compared to the actual toxicity data retrieved from the database. The results of this comparison show that generally, the classification system provides adequate predictions of either the aquatic toxicity (class 1) or the possible range of toxicity (other classes) of organic compounds. A slight underestimation of effect concentrations occurs for some highly water soluble, reactive chemicals with low log K(ow) values. On the other end of the scale, some compounds that are classified as belonging to a relatively toxic class appear to belong to the so-called baseline toxicity compounds. For some of these, additional classification rules are proposed. Furthermore, some groups of compounds cannot be classified, although they should be amenable to predictions. For these compounds additional research as to class membership and associated prediction rules is proposed.     

Bioconcentration factor of relatively low concentrations of chlorophenols in Japanese medaka

Bioconcentration factors (BCF) for pentachlorophenol (PCP) and 2,4-dichlorophenol (2,4-DCP) in Japanese medaka (Oryzias latipes) were determined at five different concentrations of the chemicals, between 0.1 and 10 microg/l (PCP), 0.3 and 30 microg/l (2,4-DCP), in the ambient water. Medaka were exposed to each chemicals in a continuous-flow system during the embryonic development period and 60 days after hatching from eggs collected in the laboratory. Both the exposure time and the aqueous concentrations are much more realistic and closer to natural aquatic environments than those used in conventional BCF studies. The BCF values of PCP were from (4.9+/-2.8)x10(3) at the aqueous concentration of 0.074+/-0.028 microg/l to (2.1+/-1.4)x10(3) at 9.70+/-0.56 microg/l. The BCF value of 2,4-DCP were from (3.4+/-3.0)x10(2) at 0.235+/-0.060 microg/l to 92+/-27 at 27.3+/-1.6 microg/l. Generally, BCF values increased as the aqueous concentrations of PCP or 2,4-DCP decreased. This finding suggests that a relatively low and realistic aqueous concentration of these compounds is necessary to more accurately determine their BCF values in natural aquatic environments. Conventional BCF experiments at higher aqueous concentrations may underestimate the BCF values.     

中国地表饮用水水源地有机类内分泌干扰物污染现况分析

有机类内分泌干扰物(EDCs)是一类对人类和生物内分泌系统产生干扰,并可造成其紊乱的特殊外来物质,对人类和生物健康有极大的危害.以与人类生活密切相关的地表饮用水水源地中的有机类EDCs为研究重点,对中国目前地表饮用水水源地EDCs污染状况、污染物种类及其来源及可能的污染途径进行了评述.目前,中国各地区地表饮用水水源地均有有机类EDCs检出.其中以有机氯农药六六六及其异构体、DDT及其代谢产物和多氯联苯检出率最高,且某些地区检测浓度相当高,主要来源是农药使用和污水排放.国内外对地表饮用水水源地EDCs突发污染事件的研究均较少,应引起高度重视.     

Daily surface UV exposure and its relationship to surface pollutant measurements

For the past 30 years, the stratospheric ozone layer has decreased in the Northern Hemisphere. The main effect of this ozone decrease was an expected increase in the UV radiation at the Earth's surface, but there has been no clear evidence of an increasing urban trend in surface UV. This study shows that specific air pollutants can reduce the increased surface levels of UV radiation and offers an explanation for why the expected surface UV increases have not been observed, especially in urban regions. A U.S. Environmental Protection Agency (EPA) UV monitoring site at the University of California at Riverside combined with air pollution data from a site operated by the California Air Resources Board in Rubidoux, CA, provided the basis of this study. The 1997 South Coast Ozone Study (SCOS-97) provided three key ingredients: black carbon, PM10 concentrations, and collocated radiometric measurements. The Total Ozone Mapping Spectrometer (TOMS) satellite data were used to provide the stratospheric ozone levels that were included in the statistical model. All of these input parameters would be used to test this study's hypothesis: the expected increase of surface UV radiation, caused by decreases in stratospheric ozone, can be masked by increases in anthropogenic emissions. The values for the pollutants were 7:00 a.m.-5:00 p.m. averages of the instrument's values taken during summer 1997. A statistical linear regression model was employed using the stratospheric ozone, black carbon, PM10, and surface ozone concentrations, and the sin (theta) and cos (theta). The angle theta is defined by theta = 2pi (Julian date/365). This model obtained a coefficient of determination of 0.94 with an uncertainty level (p value) of less than 0.3% for all of the variables in the model except ground-level ozone. The final model, regressed against a data set from a remote, western North Carolina site, resulted in a coefficient of determination of 0.92. The model shows that black carbon can reduce the Diffey-weighted UV levels that reach the surface by as much as 35%, depending on the season.     

Occurrence of UV filter compounds from sunscreens in surface waters: regional mass balance in two Swiss lakes

Consumer care products often contain UV filters, organic compounds which absorb ultraviolet light. These compounds may enter surface waters directly (when released from the skin during swimming and bathing) or indirectly via wastewater treatment plants (when released during showering or washed from textiles). Predicted and measured UV filter concentrations were compared in a regional mass balance study for two Swiss lakes: Lake Zurich, a typical midland lake which is also an important drinking water resource, and Hüttnersee, a small bathing lake. Both lakes are extensively used for recreational activities and considerable direct input of UV filters is thus expected. This input was estimated from the number of visitors at swimming areas around the lakes and a survey of the usage of sunscreen products among these visitors. Possible additional indirect input via wastewater treatment plants was not considered in this study. The quantitatively most important UV filters, as indicated by the survey data, ethylhexyl methoxycinnamate, octocrylene, 4-methylbenzylidene camphor, butyl methoxydibenzoylmethane, and benzophenone-3, all lipophilic compounds, were selected for analysis by gas chromatography-mass spectrometry. Concentrations of individual UV filters in water from Lake Zurich were low, ranging from <2 ng l(-1) (detection limit) to 29 ng l(-1), and somewhat higher at Hüttnersee, ranging from <2 to 125 ng l(-1), with the highest concentrations found in summer, consistent with direct inputs to the lakes during this time. The concentrations were clearly lower than predicted from input estimates based on the surveys. This may be in part due to (i) an overestimation of these inputs (e.g. less than the 50% wash-off of UV filters assumed to occur during swimming), and (ii) some removal of these compounds from the lakes by degradation and/or sorption/sedimentation. UV filters were also detected in semipermeable membrane devices (SPMDs) deployed at Lake Zurich and Greifensee, another midland lake, at concentrations of 80-950 ng SPMD(-1), confirming the presence of the compounds in surface waters and indicating a certain potential for bioaccumulation. SPMD-derived water concentrations were in the range of 1-10 ng l(-1) and thus corresponded well with those determined in water directly. No UV filters were detected above blank levels in SPMDs deployed at a remote mountain lake used for background measurements.     

Modelling the fate of hydrophobic organic contaminants in a boreal forest catchment: A cross disciplinary approach to assessing diffuse pollution to surface waters

The fate of hydrophobic organic compounds (HOCs) in soils and waters in a northern boreal catchment was explored through the development of a chemical fate model in a well-characterised catchment system dominated by two land types: forest and mire. Input was based solely on atmospheric deposition, dominated by accumulation in the winter snowpack. Release from soils was governed by the HOC concentration in soil, the soil organic carbon fraction and soil-water DOC content. The modelled export of selected HOCs in surface waters ranged between 11 and 250 ng day⁻¹ during the snow covered period, compared to 200 and 9600 ng/d during snow-melt; highlighting the importance of the snow pack as a source of these chemicals. The predicted levels of HOCs in surface water were in reasonable agreement to a limited set of measured values, although the model tended to over predict concentrations of HOCs for the forested sub-catchment, by over an order of magnitude in the case of hexachlorobenzene and PCB 180. This possibly reflects both the heterogeneity of the forest soils and the complicated and changing hydrology experienced between the different seasons.     

Kinetics of peat soil dissolved organic carbon release to surface water. Part 2. A chemodynamic process model

Temporary water reservoirs built upon peat soil may exhibit water quality impairment from elevated dissolved organic carbon (DOC). Microbiological decay of the organic carbon in the bed with subsequent release produces "tea" colored water which may require treatment prior to use. This paper contains a process-based mathematical model that quantifies the DOC release from the bed and its build-up in the water column. The model elements are based on microbial DOC production rates and bed sediment transport kinetics describing its' release from the organic soil systems. It relies on laboratory data obtained from an experimental study, Part 1, designed to simulate the DOC chemodynamics of aquatic reservoirs built upon peat soils. A two-step DOC release process was structured based on the experimental findings. The model mechanism assumes a quick release fraction that characterizes the upper soil surface layers as a "tea bag" type release process. This is followed by a fraction that is continuously produced and then released at a constant rate overtime by on-going microbial processes within the upper soil layers. The depth of the active layer, selected as h* = 0.3 cm, is the single adjustable parameter in the model. Concentration predictions of the are consistent with the laboratory simulations and field observations. Measured vs. model-calculated DOC concentrations for both in the microcosm bed and water column are used to test critical features of the proposed model. As conceived and structured it appears to be a realistic first step in quantifying the DOC release consequences for the water column of a reservoir sited upon a peat-soil bed. The development ends with an application to a hypothetical reservoir in order to illustrate model strengths and uncertainties.     

Developing a multimedia model of chemical dynamics in an urban area.

A multimedia model has been developed to account for the movement of semi-volatile organic compounds (SOCs) in an urban environment. The model, based on a Level III fugacity model of D. Mackay (Multimedia Environmental Models: The Fugacity Approach, Lewis Publishers, Boca Raton, FL, 1991), consists of six compartments: air, surface water, sediment, soil, vegetation, and an organic film that coats impervious surfaces. The latter is a newly identified compartment into which gas-phase SOCs partition and particle-phase SOCs are believed to be efficiently captured (M.L. Diamond, S.E. Gingrich, K. Fertuck, B.E. McCarry, G.A. Stern, B. Billeck, B. Grift, D. Brooker, T.D. Yager, Environ. Sci. Technol., 34 (2000a), 2900-2908). The model, parameterized for downtown Toronto, Ontario, Canada, and run with an illustrative emission rate for selected polycyclic aromatic hydrocarbons and homologues of polychlorinated dibenzodioxins, indicates that the film achieves the highest concentrations among media but that soils are the greatest sink for all but the least hydrophobic chemicals. The film "reflects" the more volatile chemicals into air, facilitates removal to surface waters by wash-off, and provides a surface on which photolytic degradation can occur. As such, the film is a transient sink that increases chemical mobility in urban areas by increasing air concentrations and the cycling of these compounds between air and urban surfaces and increasing water concentrations. Vegetation also accumulates SOCs, a portion of which is transferred to soil that reduces chemical mobility.