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).     

Methyl Tertiary Butyl Ether (MTBE) and Other Volatile Organic Compounds (VOCs) in Public Water Systems,Private Wells,and Ambient Groundwater Wells in New Jersey Compared to Regulatory and Human-Health Benchmarks

Potential threats to drinking water and water quality continue to be a major concern in many regions of the United States. New Jersey, in particular, has been at the forefront of assessing and managing potential contamination of its drinking water supplies from hazardous substances. The purpose of the current analysis is to provide an up-to-date evaluation of the occurrence and detected concentrations of methyl tertiary butyl ether (MTBE) and several other volatile organic compounds (VOCs) in public water systems, private wells, and ambient groundwater wells in New Jersey based on the best available data, and to put these results into context with federal and state regulatory and human-health benchmarks. Analyses are based on the following three databases that contain water quality monitoring data for New Jersey: Safe Drinking Water Information System (SDWIS), Private Well Testing Act (PWTA), and National Water Information System (NWIS). For public water systems served by groundwater in New Jersey, MTBE was detected at a concentration ≥10 μg/L, ≥20 μg/L, and ≥70 μg/L at least once in 30 (2%), 21 (1.4%), and five (0.3%) of sampled systems from 1997 to 2011, respectively. For private wells in New Jersey, MTBE was detected at a concentration ≥10 μg/L, ≥20 μg/L, and ≥70 μg/L at least once in 385 (0.5%), 183 (0.2%), and 46 (0.05%) of sampled wells from 2001 to 2011, respectively. For ambient groundwater wells in New Jersey, MTBE was detected at a concentration ≥10 μg/L, ≥20 μg/L, and ≥70 μg/L at least once in 14 (2.1%), 9 (1.3%), and 4 (0.6%) of sampled wells from 1993 to 2012, respectively. Average detected concentrations of MTBE, as well as detected concentrations at upper-end percentiles, were less than corresponding benchmarks for all three datasets. The available data show that MTBE is rarely detected in various source waters in New Jersey at a concentration that exceeds the State's health-based drinking water standard or other published benchmarks, and there is no evidence of an increasing trend in the detection frequency of MTBE. Other VOCs, such as tetrachloroethylene (PCE), trichloroethylene (TCE), and benzene, are detected more often above corresponding regulatory or human-health benchmarks due to their higher detected concentrations in water and/or greater toxicity values. The current analysis provides useful data for evaluating the nature and extent of historical and current contamination of water supplies in New Jersey and potential opportunities for public exposures and health risks due to MTBE and other VOCs on a statewide basis. Additional forensic or forecasting analyses are required to identify the sources or timing of releases of individual contaminants at specific locations or to predict potential future water contamination in New Jersey.     

Breakthrough Curves Characterization and Identification of an Unknown Pollution Source in Groundwater System Using an Artificial Neural Network (ANN)

Contamination of groundwater constrains its uses and poses a serious threat to the environment. Once groundwater is contaminated, the cleanup may be difficult and expensive. Identification of unknown pollution sources is the first step toward adopting any remediation strategy. The proposed methodology exploits the capability of a universal function approximation by a feed-forward multilayer artificial neural network (ANN) to identify the sources in terms of its location, magnitudes, and duration of activity. The back-propagation algorithm is utilized for training the ANN to identify the source characteristics based on simulated concentration data at specified observation locations in the aquifer. Uniform random generation and the Latin hypercube sampling method of random generation are used to generate temporal varying source fluxes. These source fluxes are used in groundwater flow and the transport simulation model to generate necessary data for the ANN model-building processes. Breakthrough curves obtained for the specified pollution scenario are characterized by different methods. The characterized breakthrough curves parameters serve as inputs to ANN model. Unknown pollution source characteristics are outputs for ANN model. Experimentation is also performed with different number of training and testing patterns. In addition, the effects of measurement errors in concentration measurements values are used to show the robustness of ANN based methodology for source identification in case of erroneous data.     

Variations in concentrations and compositions of polycyclic aromatic hydrocarbons (PAHs) in coals related to the coal rank and origin

The release of unburnt coal particles and associated polycyclic aromatic hydrocarbons (PAHs) may cause adverse impacts on the environment. This study assessed variations in the concentration and composition of PAHs in a set of fifty coal samples from eleven coal basins worldwide. The maximum PAH concentrations at high volatile bituminous rank were recorded in samples from a single basin. Considering the entire sample set, the highest PAH concentrations were in fact found outside of this rank range, suggesting that the maceral composition and thus the coal’s origin also influenced PAH concentrations. The examination of the PAH compositions revealed that alkylated 2-3 ring PAHs remain dominant compounds irrespective of coal rank or origin. Multivariate analysis based on PAH and maceral content, bulk and maturity parameters allowed the recognition of seven groups with different rank and origin within the coal sample set.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

Influence of Phenanthrene on Cadmium Toxicity to Soil Enzymes and Microbial Growth (5 pp)

Background Many contaminated sites contain a variety of toxicants. Risk assessment and the development of soil quality criteria therefore require information on the interaction among toxicants. Interactions between heavy metals are relatively well studied, but little is known about those between heavy metals and polycyclic aromatic hydrocarbons (PAHs). Methods 0.1 mg/kg dry soil phenanthrene alone or phenanthrene plus 10 mg/kg cadmium (Cd) were added to soil to determine the influence of phenanthrene on Cd toxicity to soil enzymes (invertase, urease, dehydrogenase and phosphatase) and microorganisms (fungi, bacteria and actinomycete) in paddy soil. Results and Discussion 0.1 mg/kg phenanthrene did not reduce the number of microorganisms. However, the addition of phenanthrene to soil with Cd enhanced the Cd toxicity to soil enzymes and microorganisms. This deleterious effect was seen to mainly affect the growth of fungi and the activity of invertase, urease and dehydrogenase. The order of combined inhibition of Cd and phenanthrene was fungi>bacteria>actinomycete. Conclusion The presence of phenanthrene might enhance the toxicity of Cd to soil microorganisms. Phenanthrene can easily be used by the soil actinomycetes as a source of carbon and energy and the finding may be supportive to the development of bioremediation techniques.     

Polycyclic aromatic hydrocarbon (PAH) deposition to and exchange at the air-water interface of Luhu, an urban lake in Guangzhou, China

Urban lakes are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs from wet and dry atmospheric deposition. Little was reported on the seasonal patterns of atmospheric deposition of PAHs under Asian monsoon climate. Bulk (dry + wet) particle deposition, air-water diffusion exchange, and vapour wet deposition of PAHs in a small urban lake in Guangzhou were estimated based on a year-round monitoring. The total PAH particle deposition fluxes observed were 0.44-3.46 μg m⁻² day⁻¹. The mean air-water diffusive exchange flux was 20.7 μg m⁻² day⁻¹. The vapour deposition fluxes of PAHs ranged 0.15-8.26 μg m⁻² day⁻¹. Remarkable seasonal variations of particulate PAH deposition, air-water exchange fluxes and vapour wet deposition were influenced by seasonal changes in meteorological parameters. The deposition fluxes were predominantly controlled by the precipitation intensity in wet season whereas by atmospheric concentration in dry season.     

Temporal and geographical genetic variation in the amphipod Melita plumulosa (Crustacea: Melitidae): Link of a localized change in haplotype frequencies to a chemical spill

Anthropogenic effects such as contamination affect the genetic structure of populations. This study examined the temporal and geographical patterns of genetic diversity among populations of the benthic crustacean amphipod Melita plumulosa in the Parramatta River (Sydney, Australia), following an industrial chemical spill. The spill of an acrylate/methacrylate co-polymer in naphtha solvent occurred in July 2006. M. plumulosa were sampled temporally between December 2006 and November 2009 and spatially in November 2009. Genetic variation was examined at the mitochondrial cytochrome c oxidase subunit I locus. Notably, nucleotide diversity was low and Tajima’s D was significantly negative amongst amphipods collected immediately downstream from the spill for 10 months. We hypothesize that the spill had a significant localized effect on the genetic diversity of M. plumulosa. Alternate explanations include an alternate and unknown toxicant or a localized sampling bias. Future proposed studies will dissect these alternatives.     

Two-stage chemical fractionation method for the analysis of elements and non-volatile inorganic ions in PM10 samples: Application to ambient samples collected in Rome (Italy)

A two-stage micro-analytical scheme for the determination of metals and ions in atmospheric particulate matter collected on only one Teflon filter was developed. In the first stage the collected particles are chemically fractionated for their solubility in a pH-buffered extracting solution; in the second stage the residue is mineralised. The major non-volatile inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, Ca²⁺, Mg²⁺) are determined in the first fraction by ion-chromatography (IC), while metals and metalloids (Al, As, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, S, Sb, Se, Si, Ti, V, Zn) are determined in both the acetate extractable and the mineralised residual fractions by inductively coupled plasma optical emission spectroscopy (ICP-OES).The procedure was applied to ambient 24-h PM₁₀ samples collected on Teflon filters during two field campaigns carried out at two sites in the area of Rome (Italy). The variations in the chemical composition of the collected particles during the two periods were interpreted in the light of the dilution properties of the lower atmosphere and of the back-trajectories of the air masses. The difference in the results between the two locations was interpreted in the light of their proximity to the emission sources. It was found that the acetate extractable and the mineralised residual fraction of some metals exhibit a different temporal pattern, suggesting the existence of different emission sources of the two fractions.     

Utilising the Synergy between Plants and Rhizosphere Microorganisms to Enhance Breakdown of Organic Pollutants in the Environment (15 pp)

Background Phytoremediation is a promising technology for the cleanup of polluted environments. The technology has so far been used mainly to remove toxic heavy metals from contaminated soil, but there is a growing interest in broadening its applications to remove/degrade organic pollutants in the environment. Both plants and soil microorganisms have certain limitations with respect to their individual abilities to remove/breakdown organic compounds. A synergistic action by both rhizosphere microorganisms that leads to increased availability of hydrophobic compounds, and plants that leads to their removal and/or degradation, may overcome many of the limitations, and thus provide a useful basis for enhancing remediation of contaminated environments.Main Features The review of literature presented in this article provides an insight to the nature of plant-microbial interactions in the rhizosphere, with a focus on those processes that are relevant to the breakdown and/or removal of organic pollutants. Due consideration has been given to identify opportunities for utilising the plant-microbial synergy in the rhizosphere to enhance remediation of contaminated environments.Results and Discussion The literature review has highlighted the existence of a synergistic interaction between plants and microbial communities in the rhizosphere. This interaction benefits both microorganisms through provision of nutrients by root exudates, and plants through enhanced nutrient uptake and reduced toxicity of soil contaminants. The ability of the plant-microbial interaction to tackle some of the most recalcitrant organic chemicals is of particular interest with regard to enhancing and extending the scope of remediation technologies.Conclusions Plant-microbial interactions in the rhizosphere offer very useful means for remediating environments contaminated with recalcitrant organic compounds.Outlook A better knowledge of plant-microbial interactions will provide a basis for improving the efficacy of biological remediations. Further research is, however, needed to investigate different feedback mechanisms that select and regulate microbial activity in the rhizosphere.     

Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da Area, Vietnam

PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962–1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1–41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.     

Application of encapsulation (pH-sensitive polymer and phosphate buffer macrocapsules): a novel approach to remediation of acidic ground water

Macrocapsules, composed of a pH-sensitive polymer and phosphate buffer, offer a novel remediation alternative for acidic ground waters. To test their potential effectiveness, laboratory experiments were carried out followed by a field trial within a coal pile runoff (CPR) acidic contaminant plume. Results of traditional limestone and macrocapsule treatments were compared in both laboratory and field experiments. Macrocapsules were more effective than limestone as a passive treatment for raising pH in well water from 2.5 to 6 in both laboratory and field experiments. The limestone treatments had limited impact on pH, only increasing pH as high as 3.3, and armoring by iron was evident in the field trial. Aluminum, iron and sulfate concentrations remained relatively constant throughout the experiments, but phosphate increased (0.15-32 mg/L), indicating macrocapsule release. This research confirmed that macrocapsules may be an effective alternative to limestone to treat highly acidic ground water.     

New cytochrome P450 1B1, 1C1, 2Aa, 2Y3, and 2K genes from Chinese rare minnow (Gobiocypris rarus): Molecular characterization,basal expression and response of rare minnow CYP1s and CYP2s mRNA exposed to the AHR agonist benzo[a]pyrene

Cytochrome P450 (CYP450) genes play an important role in catalyzing oxidative metabolism of toxicants. Recently, CYP1 subfamily were discovered and reported in fish, however, little is known regarding the CYP2 isoforms in fish. In the present study, the cDNA fragments of CYP 1B1 and 1C1 and CYP2Aa, 2Y3, and 2K of rare minnow were cloned and exhibited a high amino acid sequence identity compared with their zebrafish orthologs. Basal expression showed CYP1C1 and CYP 2Aa expression were observed in all eight tissues analyzed (liver, gill, intestine, kidney, spleen, brain, skin, and muscle). CYP 1A, and 1B1 expression was found in all tissues except for muscle and skin. However, CYP 2Y3 was expressed in liver, spleen, intestine and muscle whereas CYP 2 K in liver, kidney and intestine. 4 and 100 μg L⁻¹ Benzo[a]pyrene (BaP) induced patterns showed that CYP 1A, 1B1 and 1C1 expression in liver, gill, and intestine was strongly up-regulated (p < 0.05). Furthermore, CYP 2Y3 was strongly induced in liver from BaP treatments (p < 0.05). The high induction on mRNA level of CYP1s and CYP 2Y3 by BaP could be associated with catalyzing detoxification and indicated that CYP2s may also be potential biomarker to screen AHR agonist. The high responsiveness of CYP1 and 2 genes suggested Chinese rare minnow is feasible to screen and assess pollution with AHR agonist.     

应用自动识别和定量系统评价两种污水再生工艺对微量有机污染物的去除效果

采用气质联用分析,并结合自动识别与定量系统(AIQS-DB)考察2种再生水厂采用的深度处理工艺对微量有机污染物的去除效果。结果表明,以污水为原水的膜生物反应器(MBR)+臭氧氧化+生物活性炭滤池(BAC)工艺用于再生水生产,MBR工艺对有机污染物的去除起主要作用;城市污水厂二级出水为原水的混凝沉降+浸没式超滤(SMF)/连续微滤(CMF)+部分反渗透(RO)+臭氧氧化工艺用于再生水生产,其SMF和CMF工艺段的膜截留作用均可有效消减有机污染物含量,SMF的效果优于CMF;2种工艺中采用的臭氧技术都能进一步加强部分物质的去除效果。气质联用结合AIQS-DB可用于再生水中污染物的筛查和不同污水再生工艺对微污染物消减效果的评价。     

Application of the top specified boundary layer (TSBL) approximation to initial characterization of an inland aquifer mineralization: 1. Direct contact between fresh and saltwater

This paper presents a basic study in generalized terms that originates from two needs: (1) to understand the major mechanisms involved in the mineralization of groundwater of the Great Bend Prairie aquifer of Kansas by saltwater originating from a deeper Permian bedrock formation, and (2) to develop simple, robust tools that can readily be used for local assessment and management activities in the salt-affected region. A simplified basic conceptual model is adopted, incorporating two horizontal layers of porous medium which come into contact at a specific location within the model domain. The top layer is saturated with freshwater, and the bottom layer is saturated with saltwater. The paper considers various stages of approximation which can be useful for simplified simulation of the build-up of the transition zone (TZ) between the freshwater and the saltwater. The hierarchy of approximate approaches leads to the development of the top specified boundary layer (TSBL) method, which is the major tool used in this study for initial characterization of the development of the TZ. It is shown that the thickness of the TZ is mainly determined by the characteristic dispersivity. The build-up of the TZ is completed after a time period equal to the time needed to advect a fluid particle along the whole extent of the TZ. Potential applications and the effects of natural recharge and pumpage on salinity transport in the domain are discussed and evaluated in the context of demonstrating the practicality of the TSBL approach.