Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

Concentration of organic micropollutants in the atmosphere of Trieste, Italy

Purpose

PCDD/Fs, PCBs, and PAHs, ubiquitous environmental pollutants which are part of the POPs, are mainly produced by anthropogenic activities as well as by natural processes. Occurrences of these pollutants in different sites in Trieste are presented. PCDD/Fs distribution and their possible emission sources are discussed.

Methods

Air samples were collected in different sites near the industrial area, in the city center, and in a background area, using a high-volume sampler equipped with a quartz fiber filter and a PUF. Each sampling lasted a week.

Results

The concentrations of the organochlorinated pollutants are consistent with literature data (??PCDD/Fs and ??dl-PCBs were 5?C38?fg TEQ/Nm³ and 4?C31?fg TEQ/Nm³, respectively), and an apparent seasonal trend was found with slightly higher concentrations in the winter and lower levels in both summer campaigns. Moreover, the isomer profile of each sampling campaign was compared to the fingerprint of a sintering plant, a cement plant, and an incinerator, the main industrial activities in Trieste.

Conclusions

The organic micropollutants were detected in levels consistent with literature data. The results show that the pollutants are uniformally distributed in the atmosphere of Trieste. PCDD/F fingerprints in each site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby sintering plant.     

In situ modification of an aquifer material by a cationic surfactant to enhance retardation of organic contaminants

Sorption of hexadecyltrimethylammonium chloride (HDTMA), a cationic surfactant, on aquifer material from Columbus AFB, Mississippi, U.S.A., was examined. Transport studies using flow-through columns and a box model aquifer showed that an almost stationary zone of HDTMA-modified aquifer material could be produced in situ without a significant decrease in hydraulic conductivity.Perchloroethylene (PCE) and naphthalene sorption isotherms on the HDTMA-modified aquifer material were linear, and sorption coefficients were increased by over two orders of magnitude relative to the unmodified material. The retardation of PCE by insitu emplaced HDTMA zones within a column was examined. Agreement between batch- and column-derived sorption coefficients and breakthrough curve symmetry indicates that local equilibrium was attained. Significant retardation of a naphthalene plume by an in situ emplaced surfactant zone was demonstrated in the box model aquifer system.The experimental results indicate that it is feasible to create in situ a sorbent zone within an aquifer using cationic surfactants. In most situations, the sorbent zone concept needs to be coupled with contaminant degradation processes for sorbent emplacement to be a practical tool in the remediation of groundwater contamination sites. Sorbent zones may be of benefit in the engineering of suitable environments for microbial or abiotic degradation reactions and by providing time slow reactions to occur.     

Environmental and biological monitoring of occupational exposure to organic micropollutants in gasoline.

An exposure risk assessment of workers in a refinery production unit was undertaken. Gasoline and its main components were investigated through environmental and biological monitoring. Measured variables were environmental benzene, toluene, pentane and hexane; benzene and toluene in blood and urine; tt-MA (metabolite of benzene) in urine. Multivariate statistical analysis of the data showed that worker's exposure to the above substances fell within the limits specified by organisations such as ACGIH. Also, biological values complied with reference values (RV) for non-occupationally-exposed population. Different values of biological variables were determined by separating smokers from non-smokers: smokers had hematic and urinary benzene values significantly higher than non-smokers. During a 3-yr sampling, it was possible to identify a significant decrease of benzene in the workplace air and of hematic benzene for non-smokers. The most exposed department, one in which tank-lorries were loaded, needs further investigation and extended monitoring.     

Survey regarding the occurrence of selected organic micropollutants in the groundwaters of overseas departments

To collect a complete dataset regarding the occurrence of organic substances in groundwater, this study presents the examination of 66 organic contaminants in the groundwater of overseas departments, including pesticides, pharmaceutical compounds, hormones and some industrial substances. The selective and sensitive analytical methods are described. These techniques begin with solid-phase extraction (SPE) followed by analysis using liquid chromatography–tandem mass spectrometry (LC-MS/MS) and gas chromatography–mass spectrometry (GC-ToF-MS). The paper summarises the analytical results from 40 sampling points collected during two campaigns in Guadeloupe, Martinique, Reunion, Mayotte and Guiana, representing 80 samples. Of the 66 target substances, 36 were determined at least once. Among the most frequently detected are bisphenol A (frequency, 96 %; max., 7,400 ng/L), caffeine (frequency, 91 %; max., 1,240 ng/L), pentachlorophenol (frequency, 55 %; max., 418 ng/L), and carbamazepine (frequency, 56 %; max., 22 ng/L). The results do not put in evidence that the origin of the sample or climatic characteristics of these regions influence the dilution and release of micropollutants.     

Influence of contaminated particles on the bioaccumulation of hydrophobic organic micropollutants in fish

The influence of contaminated particles on the bioconcentration of hydrophobic chemicals by fish is dependent on the hydrophobicity of the chemicals. This has been shown for polychlorinated benzenes and biphenyls (ranging over three orders of magnitude in octan-1-ol/water partition coefficient) which are sorbed on very low organic carbon content particles. For chemicals with low to moderate hydrophobicity, the amount of the chemical which is sorbed, relative to the amount which is dissolved, determines the influence that contaminated particles have on the uptake of the chemicals by fish. In this present experiment, for lower chlorinated benzenes and biphenyls, the amount dissolved in water are high compared with the amounts which are present in the sorbed state, and the influence of contaminated particles on their uptake by fish is negligible. For more hydrophobic chemicals, which have lower aqueous solubilities, such as penta and hexachlorobenzene, and tri and tetrachlorobiphenyls, contaminated particles can have a much greater influence on the uptake by fish. If the number of contaminated particles is sufficiently high, the low aqueous solubilities, in combination with relatively high rates of desorption or dissolution, enable the particles to act as a source of the hydrophobic chemicals. For extremely hydrophobic chemicals, the rates of dissolution or desorption determine the rates of uptake of the chemical by the fish. Hence, during relatively short periods of exposure, there is no influence of contaminated particles on the bioaccumulation.     

Review of passive accumulation devices for monitoring organic micropollutants in the aquatic environment

Over the past 15 years passive sampling devices have been developed that accumulate organic micropollutants and allow detection at ambient sub ng/l concentrations. Most passive accumulation devices (PADs) are designed for 1-4 weeks field deployment, where uptake is governed by linear first order kinetics providing a time weighted average of the exposure concentration. Semipermeable membrane devices (SPMDs) are the most comprehensively studied PADs, but other samplers may also be considered for aquatic monitoring purposes. The applicability of the PADs is reviewed with respect to commonly monitored aqueous matrices and compounds, the detection limits, and for use in quantitative monitoring related to requirements embedded in the EU Water Framework Directive, the US and EU Water Quality Criteria, and the Danish monitoring aquatic programme. The PADs may monitor >75% of the organic micropollutants of the programmes. Research is warranted regarding the uptake in PADs in low flow environments and for the development of samplers for polar organic compounds.     

Distribution of metals in a polluted aquifer: A comparison of aquifer suspended material to fine sediments of the adjacent environment

Metal concentrations were determined for groundwater suspended matter from a site in the coastal aquifer of Israel which has been irrigated with secondary sewage effluents since the 1960's. Suspended matter was collected from the aquifer saturated zone by pumping and by a multi-layer sampler. Fine sediments were collected from both the unsaturated and saturated zones of the contaminated aquifer, as well as from an adjacent uncontaminated environment. Ag, Cu, Fe, Mn and Zn were leached from the samples in three sequential chemical extractions which are taken to represent the carbonate, organic and oxide phases. Comparison of the aquifer samples to those of the adjacent environment showed that Fe and Mn are primarily enriched in non-mobile fine sediments and not in suspended matter, whereas the concentrations of Zu, Cu and Ag show up to an order of magnitude enrichment in the mobile suspended matter in groundwater. The enrichment of these metals in the suspended matter indicates that metals from sewage effluents and agricultural activities have reached the groundwater.     

Field and laboratory studies of the fate and enantiomeric enrichment of venlafaxine and O-desmethylvenlafaxine under aerobic and anaerobic conditions

The stereoselectivity of R,S-venlafaxine and its metabolites R,S-O-desmethylvenlafaxine, N-desmethylvenlafaxine, O,N-didesmethylvenlafaxine, N,N-didesmethylvenlafaxine and tridesmethylvenlafaxine was studied in three processes: (i) anaerobic and aerobic laboratory scale tests; (ii) six wastewater treatment plants (WWTPs) operating under different conditions; and (iii) a variety of wastewater treatments including conventional activated sludge, natural attenuation along a receiving river stream and storage in operational and seasonal reservoirs. In the laboratory and field studies, the degradation of the venlafaxine yielded O-desmethylvenalfaxine as the dominant metabolite under aerobic and anaerobic conditions. Venlafaxine was almost exclusively converted to O-desmethylvenlafaxine under anaerobic conditions, but only a fraction of the drug was transformed to O-desmethylvenlafaxine under aerobic conditions. Degradation of venlafaxine involved only small stereoisomeric selectivity. In contrast, the degradation of O-desmethylvenlafaxine yielded remarkable S to R enrichment under aerobic conditions but none under anaerobic conditions. Determination of venlafaxine and its metabolites in the WWTPs agreed well with the stereoselectivity observed in the laboratory studies. Our results suggest that the levels of the drug and its metabolites and the stereoisomeric enrichment of the metabolite and its parent drug can be used for source tracking and for discrimination between domestic and nondomestic wastewater pollution. This was indeed demonstrated in the investigations carried out at the Jerusalem WWTP.     

Evaluation of a serum bottle technique for assessing the anaerobic biodegradability of organic chemicals under methanogenic conditions

The serum bottle method of Shelton and Tiedje (1984), for assessing the potential of an organic chemical to undergo anaerobic biodegradation, was evaluated using U.K. primary digesting sludges. The method was modified by using the sludge at a known solids content and employing sterile (autoclaved) controls to correct for abiotic gas production. Gas production was measured with a compact hand-held pressure meter, which represented an improvement over previously described techniques. Results obtained confirmed the reliability and precision of this type of simple, screening test for assessing anaerobic biodegradability. However, the test is only applicable to low-sulphate, methanogenic environments and evidence is presented of interference from sulphate-reducing bacteria (SRB) when testing sulphate-containing chemicals.     

The contribution of selected organic substrates to the anaerobic cometabolism of sulfamethazine

Biodegradation of organic micropollutants is likely to occur due to cometabolism by particular microbial groups. In an effort to identify the stages of anaerobic digestion potentially involved in the biodegradation of the veterinary antimicrobial sulfamethazine (SMZ), the influence of selected carbon sources (sucrose, glucose, fructose, ethanol, meat extract, cellulose, soluble starch, soy oil, acetic acid, propionic acid and butyric acid) on SMZ removal by anaerobic sludge was evaluated in short-term batch experiments. Adsorption to the granular sludge constituted a significant removal mechanism, accounting for 39% of SMZ removal in control experiments. The presence of glucose, fructose, sucrose and meat extract exerted an inducing effect on SMZ degradation, resulting in removal efficiencies of 54, 53, 58 and 61%, respectively, indicating the occurrence of cometabolism. Time courses of sucrose and meat extract degradation revealed markedly distinct organic acid profiles but resulted in similar SMZ removals. Temporal profiles of acetic and propionic acid degradation were not associated with SMZ removal, as changes in SMZ concentration were observed even after the organic acids had been completely removed. The experimental results suggest that SMZ cometabolism is not associated to sucrose hydrolysis, acetoclastic methanogenesis and acetogenesis from propionic acid.     

Biological degradation of triclocarban and triclosan in a soil under aerobic and anaerobic conditions and comparison with environmental fate modelling

Triclocarban and triclosan are two antimicrobial agents widely used in many personal care products. Their biodegradation behaviour in soil was investigated by laboratory degradation experiments and environmental fate modelling. Quantitative structure-activity relationship (QSAR) analyses showed that triclocarban and triclosan had a tendency to partition into soil or sediment in the environment. Fate modelling suggests that either triclocarban or triclosan "does not degrade fast" with its primary biodegradation half-life of "weeks" and ultimate biodegradation half-life of "months". Laboratory experiments showed that triclocarban and triclosan were degraded in the aerobic soil with half-life of 108 days and 18 days, respectively. No negative effect of these two antimicrobial agents on soil microbial activity was observed in the aerobic soil samples during the experiments. But these two compounds persisted in the anaerobic soil within 70 days of the experimental period.     

A review of the conditions leading to downwash in physical modeling experiments

Although stack downwash is not a widespread problem at modern fossil-fuel power plants and larger industrial stacks, it is a very important problem in simulating buoyant plumes in wind tunnels and towing tanks. Scaling criteria for avoiding downwash in ten subcritical model experiments have been reviewed. A comparison was made between data on the occurrence of downwash from 10 modeling studies to the theory proposed by Tatom (1986). In general, there was good agreement of Tatom's theory with the occurrence of downwash.     

Profile analysis of organic micropollutants in the environment of a coal burning area, NW Greece

The concentrations and profiles of dibenzo-p-dioxins, dibenzofurans, polychlorinated biphenyls and polynuclear aromatic compounds in various environmental matrices are presented in this study. The examined environmental matrices are total suspended particles, fly ash and soil collected in NW Greece, an area characterized by intensive coal burning for electrical power generation. Moreover, the occurrence of organic micropollutants in soot after an accidental fire was examined and the possible impact on the outdoor environment was evaluated. Results were statistically treated to obtain information on representative PCDD/F profiles in each matrix and to compare these profiles with the compositional patterns of possible sources from literature. Coal combustion, fly ash and vehicle exhausts appeared to be the most possible sources in local atmosphere.     

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.     

Priority organic micropollutants in water sources in Flanders and the Netherlands and assessment of removal possibilities with nanofiltration

The occurrence of organic micropollutants in ground- and surface waters has become an important concern for the drinking water industry, mainly because of possible related health effects. Due to the polar nature of some of these pollutants, they are not completely removed by traditional water treatment barriers. This paper offers an overview of priority organic micropollutants and their occurrence in Flemish and Dutch water sources. Furthermore, rejection by nanofiltration is qualitatively predicted for the selected priority micropollutants. The qualitative prediction is based on the values of key solute and membrane parameters in nanofiltration. Predicted values are then compared with experimental values obtained from literature. Overall, the qualitative predictions are roughly in agreement with literature values. Prediction based on key parameters may thus prove to be a very quick and useful technique to assess the implementation of nanofiltration as a treatment step for organic micropollutants in drinking water plant design.     

The removal of microorganisms and organic micropollutants from wastewater during infiltration to aquifers after irrigation of farmland in the Tula Valley, Mexico

The Tula Valley receives untreated wastewater from Mexico City for agricultural irrigation, half of which infiltrates to aquifers from where drinking water is extracted. Samples of wastewater and infiltrated water from three areas of the valley were analyzed for microorganisms, organic micropollutants, and some basic parameters. Concentrations of microorganisms in the infiltrated water were generally very low but the incidence of fecal coliforms (present in 68% of samples), somatic bacteriophages (36%), Giardia spp. (14%), and helminth eggs (8%) suggested a health risk. Organic micropollutants, often present at high concentrations in the wastewater, were generally absent from the infiltrated water except carbamazepine which was in 55% of samples (up to 193 ng/L). There was no correlation between carbamazepine concentrations and the presence of microorganisms but highest concentrations of carbamazepine and boron coincided. A treatment such as nanofiltration would be necessary for the infiltrated water to be a safe potable supply.     

污泥厌氧消化在游离氨调控下强化磷与有机物释放的作用效果

基于污泥资源化与能源化的目的,采用游离氨调控的方式,利用系统中有机质提高沼气中甲烷体积分数的同时分析系统中磷浓度和形态的变化情况。结果表明,与空白阶段相比,游离氨调控后系统中溶解性蛋白、多糖质量浓度分别提升16.34%和26.43%;沼气中甲烷平均体积分数由73.61%提升至85.04%。通过三维荧光光谱(3D-EEM)和平行因子法(PARAFAC)分析两个反应阶段厌氧污泥上清液,芳香类蛋白质Ⅰ占比分别从35%、47%下降至29%与40%。这表明经过游离氨调控后芳香类蛋白质Ⅰ利用效果略有提高。在磷形态分析方面,游离氨调控使得进出水总磷、磷酸盐质量浓度分别提升948.64%、1 219.35%、2 254.55%与2 280%,磷释放效果明显。根据X 射线能量色散谱(EDS)、傅里叶红外光谱(FTIR)与X射线光电子能谱(XPS) 分析结果表明,污泥中P主要与Fe、Al等金属元素以复合盐的形式存在;并在厌氧消化过程中发生了一定比例的磷形态转化。但游离氨诱导磷形态转化的机理仍需进一步探究。该研究结果进一步表明游离氨在厌氧消化过程中调控强化了有机物的利用效果,促进磷的释放与形态变化。该研究结果可为基于游离氨调控下有机物与磷的释放提供参考。