Calibration of the Chemcatcher passive sampler for the monitoring of priority organic pollutants in water

An integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low-density polyethylene diffusion membrane was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polyaromatic hydrocarbons and organochlorine pesticides, in water. The effect of temperature and water turbulence on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water was studied in a flow-through system under controlled conditions. It was found that the absorption of test analytes from water to the sampler is related to their desorption to water. This allows for the in situ calibration of the uptake of pollutants using offload kinetics of performance reference compounds. The sampling kinetics are dependent on temperature, and for most of the tested analytes also on the flow velocity. Sampler-water partition coefficients did not significantly change with temperature.     

Modelling and field application of the Chemcatcher passive sampler calibration data for the monitoring of hydrophobic organic pollutants in water

Passive sampling of dissolved pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low density polyethylene membrane, was developed and calibrated for the measurement of time weighted average (TWA) concentrations of hydrophobic pollutants in water. In this study, the exchange kinetics were modelled to obtain a better understanding of the mechanism of the accumulation process and to enable the measurement of TWA concentrations of hydrophobic pollutants in the field. An empirical relationship that enables the calculation of in situ sampling rates of chemicals using performance reference compounds was derived and its application was demonstrated in a field study in which TWA aqueous concentrations estimated from sampler data for target analytes were compared with TWA concentrations obtained from spot samples of water collected regularly during the sampler deployment period.     

Calibration and field performance of membrane-enclosed sorptive coating for integrative passive sampling of persistent organic pollutants in water

Membrane-enclosed sorptive coating (MESCO) is a miniaturised monitoring device that enables integrative passive sampling of persistent, hydrophobic organic pollutants in water. The system combines the passive sampling with solventless preconcentration of organic pollutants from water and subsequent desorption of analytes on-line into a chromatographic system. Exchange kinetics of chemicals between water and MESCO was studied at different flow rates of water, in order to characterize the effect of variable environmental conditions on the sampler performance, and to identify a method for in situ correction of the laboratory-derived calibration data. It was found that the desorption of chemicals from MESCO into water is isotropic to the absorption of the analytes onto the sampler under the same exposure conditions. This allows for the in situ calibration of the uptake of pollutants using elimination kinetics of performance reference compounds and more accurate estimates of target analyte concentrations. A field study was conducted to test the sampler performance alongside spot sampling. A good agreement of contaminant patterns and water concentrations was obtained by the two sampling techniques.     

Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978?r ²?r ²?-1 level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.     

Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Application of System Dynamics technique to simulate the fate of persistent organic pollutants in soils

Persistent organic pollutants (POPs) are within the most dangerous pollutants released into the environment by human activities. Due to their resistance to degradation (chemical, biological or photolytic), it is critical to assess the fate and environmental hazards of the exchange of POPs between different environmental media.System Dynamics enables to represent complex systems and analyze their dynamic behavior. It provides a highly visual representation of the structure of the system and the existing relationships between the several parameters and variables, facilitating the understanding of the behavior of the system. In the present study the fate of γ-hexachlorocyclohexane (lindane) in a contaminated soil was modeled using the Vensim® simulation software.Results show a gradual decrease in the lindane content in the soil during a simulation period of 10 years. The most important route affecting the concentrations of the contaminant was the biochemical degradation, followed by infiltration and hydrodynamic dispersion. The model appeared to be highly sensitive to the half-life of the pollutant, which value depends on environmental conditions and directly affects the biochemical degradation.     

Effect of temperature, gas phase composition, pH and microbial activity on As, Zn, Pb and Cd mobility in selected soils in the Ebro and Meuse Basins in the context of global change

This study estimates the effect of environmental parameters on the mobility of four inorganic contaminants (As, Zn, Pb and Cd) in soils from three areas in the Ebro and Meuse River basins, within the context of global change. An experimental method, applicable to various soil systems, is used to measure the effect of four global-change-sensitive parameters (temperature, gas phase composition, pH and microbial activity). The aqueous phase of batch incubations was sampled regularly to monitor toxic element concentrations in water. Statistical processing enabled discrimination of the most relevant variations in dissolved concentrations measured at different incubation times and under different experimental conditions. Gas phase composition was identified as the most sensitive parameter for toxic element solubilization. This study confirms that total soil concentrations of inorganic pollutants are irrelevant when assessing the hazard for ecosystems or water resource quality.     

Atmospheric deposition, retention, and stream export of dioxins and PCBs in a pristine boreal catchment

The mass-balance between diffuse atmospheric deposition of organic pollutants, amount of pollutants retained by the terrestrial environment, and levels of pollutants released to surface stream waters was studied in a pristine northern boreal catchment. This was done by comparing the input of atmospheric deposition of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and PCBs with the amounts exported to surface waters. Two types of deposition samplers were used, equipped with a glass fibre thimble and an Amberlite sampler respectively. The measured fluxes showed clear seasonality, with most of the input and export occurring during winter and spring flood, respectively. The mass balance calculations indicates that the boreal landscape is an effective sink for PCDD/Fs and PCBs, as 96.0-99.9 % of received bulk deposition was retained, suggesting that organic pollutants will continue to impact stream water in the region for an extended period of time.     

Geno-toxicity assay of sediment and water samples from the Upper Silesia post-mining areas, Poland by means of Allium-test

Genotoxic potential of two environmental compartments (water and sediment) from the Upper Silesia Coal Basin (USCB), Poland were evaluated and compared by employing root meristem cells of Allium cepa. The clear genotoxic effect of water and sediment sampled was shown, with an important contribution of severe types of cytogenetic abnormalities. The most biologically relevant pollutants were revealed through multivariate statistical analysis of relationships between biological effects registered and the environment contamination. Overall, results of simultaneous use of conventional monitoring methods and biological tests suggested that contemporary levels of persistent pollutants in post-mining areas of the USCB may enhance the risk both for human health and biological components of natural ecosystems.     

底泥污染物释放动力学研究

采用模拟试验方式和新型微生物数量测定方法 ,研究了沼泽化湖泊底泥和受污染河流底泥在不同扰动状态下 ,底泥耗氧速率、氮和磷污染物释放动力学过程。结果表明 :( 1)底泥耗氧速率是同样条件下上覆水耗氧速率的 48倍 ,而在扰动状态下 ,底泥耗氧速率达到上覆水耗氧速率的 5 96— 93 6倍 ,扰动底泥显著增大其耗氧速率 ,底泥污染越严重 ,其耗氧速率越大 ,对水体产生的影响也越大。 ( 2 )扰动底泥可以显著增大底泥的氮磷释放速率 ,氮的释放受有机氮的氨化、氨氮的硝化、硝酸盐氮的反硝化以及氨氮被微生物吸收转化为有机氮等的影响 ;磷的释放过程受厌氧过程和底泥颗粒吸附的影响 ,耗氧速率高的底泥具有更大的氮磷释放潜力。 ( 3 )微生物数量在底泥污染物释放动力学中起着关键性作用 ,新型方法可以快速检测微生物总量。试验结果对于水环境的管理、受污染水体的修复 ,以及底泥的处理处置等都具有重要的指导意义     

Simultaneous decontamination of hexavalent chromium and methyl tert-butyl ether by UV/TiO2 process

Hexavalent chromium and methyl tert-butyl ether (MTBE) are two important environmental pollutants. Simultaneous decontamination of Cr(VI) and MTBE was studied by UV/TiO2 process. The influences of pH and the concentrations of pollutants on the kinetics of the photocatalytic reactions were evaluated. Dark adsorption tests showed that the acidic pH favored the adsorption of Cr(VI) while neutral pH favored the adsorption of MTBE. Under UV irradiation, Cr(VI) reduction was observed in Cr(VI)/TiO2 system, and MTBE oxidation was observed in MTBE/TiO2 system. The system containing Cr(VI) and MTBE by UV/TiO2 process demonstrated the synergistic effect between oxidation of MTBE and reduction of Cr(VI). The results demonstrated that two pollutants Cr(VI) and MTBE could be eliminated simultaneously by UV/TiO2 process. tert-Butyl formate, tert-butyl alcohol and acetone were identified as primary degradation products of MTBE by gas chromatography-mass spectrometry in the degradation of MTBE by UV/TiO2 process.     

Radial diffusive sampler for the determination of 8-h ambient ozone concentrations

The 8-h ozone radial diffusive sampler was evaluated according to the CEN protocol for the validation of diffusive samplers. All the parameters regarding the sampler characteristics were found to be consistent with the requirements of this protocol apart from the blank value, which must be evaluated and subtracted at each sampling. The nominal uptake rate was determined in laboratory conditions. However, the uptake rate depends on the mass uptake, temperature, humidity and on the combination of temperature and humidity. Based on laboratory experiments, an empirical model has been established which improved the agreement between the radial sampler and the reference method. This improvement was observed under several different meteorological and emission conditions of sampling. By using the model equation of uptake rate, the data quality objective of 30% for the expanded uncertainty included in the O(3) European Directive, is easily attained. Therefore, the sampler represents an appropriate indicative method.     

Physiological and foliar symptom response in the crowns of Prunus serotina, Fraxinus americana and Acer rubrum canopy trees to ambient ozone under forest conditions

The crowns of five canopy dominant black cherry (Prunus serotina Ehrh.), five white ash (Fraxinus americana L.), and six red maple (Acer rubrum L.) trees on naturally differing environmental conditions were accessed with scaffold towers within a mixed hardwood forest stand in central Pennsylvania. Ambient ozone concentrations, meteorological parameters, leaf gas exchange and leaf water potential were measured at the sites during the growing seasons of 1998 and 1999. Visible ozone-induced foliar injury was assessed on leaves within the upper and lower crown branches of each tree. Ambient ozone exposures were sufficient to induce typical symptoms on cherry (0-5% total affected leaf area, LAA), whereas foliar injury was not observed on ash or maple. There was a positive correlation between increasing cumulative ozone uptake (U) and increasing percent of LAA for cherry grown under drier site conditions. The lower crown leaves of cherry showed more severe foliar injury than the upper crown leaves. No significant differences in predawn leaf water potential (psi(L)) were detected for all three species indicating no differing soil moisture conditions across the sites. Significant variation in stomatal conductance for water vapor (g(wv)) was found among species, soil moisture, time of day and sample date. When comparing cumulative ozone uptake and decreased photosynthetic activity (P(n)), red maple was the only species to show higher gas exchange under mesic vs. drier soil conditions (P < 0.05). The inconsistent differences in gas exchange response within the same crowns of ash and the uncoupling relationship between g(wv) and P(n) demonstrate the strong influence of heterogeneous environmental conditions within forest canopies.     

BTEX determination in water matrices using HF-LPME with gas chromatography-flame ionization detector

In the present work, a sample pre-treatment technique for the determination of trace concentrations of benzene, toluene, ethyl benzene and xylene (BTEX) in aqueous samples has been developed and applied to analysis of the selected analytes in environmental water samples. The extraction procedure is based on coupling polypropylene hollow-fiber liquid phase microextraction (HF-LPME) with gas chromatography by flame ionization detection (GC-FID). The effective parameters such as organic solvent, extraction time, agitation speed and salting effect were investigated. Good reproducibilities of the extraction performance were obtained, with the RSD values ranging from 2.02 to 4.61% (n=5). The method provided 41.47-128.01 fold preconcentration of the target analytes. The limits of detections for the BTEX were in the range of 0.005-03microg ml(-1). In addition, sample clean-up was achieved during LPME due to the selectivity of the hollow fiber, which prevented undesirable large molecules from being extracted. Real samples (River and waste waters) containing BTEX were examined using this method with good linearity and precision (RSDs most lower than 6.00%, n=5). All experiments were carried out at room temperature, 22+/-0.5 degrees C.     

Calibration and field application of a solvent-based cellulose membrane passive sampling device for the monitoring of polar herbicides

A passive sampler device selective for hydrophilic analytes was constructed from cellulose membrane (40microm thickness) pre-stained with ruthenium red for 96-168h to impede degradation of the cellulose. The sampling device consisted of pre-stained cellulose membrane tubing containing a binary mixture of the solvents 1-dodecanol and 2,2,4-trimethylpentane as the sequestering medium. A laboratory flow-through system was used to investigate the rates of uptake of herbicides into the solvent mixture of the device and their release. The target herbicides were diuron, atrazine, metolachlor and molinate. Uptake of the herbicides into the solvent mixture of the cellulose membrane device was linear for up to 22 days, and daily sampling rates were determined. Release half-lives from the solvent mixture of the sampling device varied from 14 days for diuron, 15 days for atrazine, 84 days for metolachlor and 28 days for molinate. A field study was undertaken to determine if herbicide concentrations in agricultural drainage water derived from the passive sampler devices deployed for periods from 7 to 22 days, using the laboratory-derived sampling rates, would compare closely with time-weighted average herbicide concentrations determined from extractions of daily composite water samples. The concentrations of diuron, atrazine, metolachlor and molinate determined using the cellulose membrane devices were within twofold of the cumulated mean of the daily drainage water extractions.     

Three-dimensional simulation of reservoir temperature and pollutant transport by the lattice Boltzmann method

Predicting the three-dimensional (3D) transport processes of reservoir temperature and pollutants is essential for water environmental protection and restoration, and introducing the lattice Boltzmann (LB) method into this prediction is necessary because of its simple algorithm, straightforward implementation of boundary conditions, and high computation efficiency. In this paper, a triple-distribution function (TDF) LB model for flow-temperature-concentration coupling simulations is introduced. Some essential techniques for implementing this method in 3D reservoirs are also described, including the treatment of water surface fluctuation, the consideration of surface heat exchange, and the hardware acceleration using the graphics processing unit (GPU). Two cases verified the proposed model, and then, the temporal-spatial variations of flow, temperature, and pollutants in the upper reservoir of a pumped-storage power station during both pumping and generating modes were analyzed to demonstrate its applicability. In the reservoir, the water forms several circulations, the cold water from the inlet flows as an undercurrent firstly, and then spread laterally, and the spreading of pollutants directly relates to the flow velocity. The results of flow, temperature, and concentration fields in different working conditions are consistent with model tests and physical laws, which shows good prospects of the proposed LB model.

     

Impact of land use changes on water quality in headwaters of the Three Gorges Reservoir

The assessment of spatial and temporal variation of water quality influenced by land use is necessary to manage the environment sustainably in basin scales. Understanding the correlations between land use and different formats of nonpoint source nutrients pollutants is a priority in order to assess pollutants loading and predicting the impact on surface water quality. Forest, upland, paddy field, and pasture are the dominant land use in the study area, and their land use pattern status has direct connection with nonpoint source (NPS) pollutant loading. In this study, two land use scenarios (1995 and 2010) were used to evaluate the impact of land use changes on NPS pollutants loading in basins upstream of Three Gorges Reservoir (TGR), using a calibrated and validated version of the soil and water assessment tool (SWAT) model. The Pengxi River is one of the largest tributaries of the Yangtze River upstream of the TGR, and the study area included the basins of the Dong and Puli Rivers, two major tributaries of the Pengxi River. The results indicated that the calibrated SWAT model could successfully reproduce the loading of NPS pollutants in the basins of the Dong and Puli Rivers. During the 16-year study period, the land use changed markedly with obvious increase of water body and construction. Average distance was used to measure relative distribution patterns of land use types to basin outlets. Forest was mainly distributed in upstream areas whereas other land use types, in particular, water bodies and construction areas were mainly distributed in downstream areas. The precipitation showed a non-significant influence on NPS pollutants loading; to the contrary, interaction between precipitation and land use were significant sources of variation. The different types of land use change were sensitive to NPS pollutants as well as land use pattern. The influence of background value of soil nutrient on NPS pollutants loading was evaluated in upland and paddy field. It was found that total nitrogen (TN) and total phosphorous (TP) in upland were more sensitive to NPS pollutants loading than in paddy fields. The results of this study have implications for management of the TGR to reduce the loading of NPS pollutants into downstream water bodies.     

Influence of rate-limited sorption on the cleanup of layered soils by vapor extraction

The conditions under which rate-limited sorption is important for cleanup of layered soils by vapor extraction are investigated. The investigation includes two steps: (a) the cleanup time is estimated for a number of scenario cases by means of a numerical model and (b) the numerical results are approximated using analytical solutions derived for simplified models. In this way, equations are derived, which give insight into the influence of different parameters characterizing the properties of the soil, the geometry of the formation, the mass transfer mechanisms in it, and the distribution of the contaminant mass in the different phases (gas phase, water phase and solid phase). The numerical model used is based on the advection-dispersion differential equations for Darcian isothermal airflow, local equilibrium contaminant mass transfer between gas phase and soil water and first-order kinetics for mass transfer between soil water and solid phase. The numerical results are approximated combining an analytical solution to estimate cleanup time in layered formations for local equilibrium sorption, which has been presented in a previous work (J. Contam. Hydrol., 36 (1999) 105). with an analytical solution based on the well-mixed reservoir model under consideration of rate-limited sorption. The analytical approximation of the cleanup time is in reasonable agreement with the numerical results and allows its estimation with small computational effort.