Application of a Dialysis Sampler to Monitor Phytoremediation Processes

A cylindrical dialysis sampler (1.2 m in length; 5 cm in diameter) was designed and constructed to sample small–scale phytoremediation processes in the root zone of poplar trees. The study site was a 183–tree plantation of hybrid poplars located at Aberdeen Proving Ground, Maryland, at the J–Field Area of Concern. The grove was planted in 1996 to intercept a chlorinated solvent plume containing 1,1,2,2–tetrachloroethane (1,1,2,2–TeCA, trichloroethene (TCE) and daughter products. Two dialysis samplers were installed: one directly in the poplar grove (approximately 0.3 m from the trunk of a mature tree) and the other outside of the grove but in the plume. Data collected included concentrations of chlorinated VOCs, organic acids, chloroacetic acids, Cl⁻, and dissolved gases (ethane, ethene, CH₄, CO₂). At the control location, the VOC profile was dominated by cis– 1,2–dichloroethene (cis–1,2–DCE) and trans–1,2–dichloroethene (trans–1,2–DCE) with concentrations ranging from 0.88-4.5 to 4.4-17.6 mg/L, respectively. Concentrations of VOCs were similar across the vertical profile. At the tree location, 1,1,2,2–TeCA and TCE were the dominant VOCs detected but as opposed to the control location were highly variable within the root zone, with the greatest variability associated with locations in the sampler where roots were observed. This highly variable profile at the tree location is indicative of VOC rhizosphere biodegradation and uptake near the active roots. This variability appears to be on the centimeter scale, emphasizing the importance of these high–resolution samplers for the study of rhizosphere influences.     

Conjunctive Vadose and Saturated Zone Monitoring for Subsurface Contamination

A comprehensive subsurface monitoring program should include contaminant detectors in both the vadose and saturated zones. Vadose zone detectors can provide an early warning of an impending groundwater contamination problem, and also yield information relevant to placing groundwater monitoring wells. Moisture probes, gas monitoring wells, and pore-liquid samplers deployed in the vadose zone complement groundwater detection wells. The objective(s) of a monitoring program, spatial-scales, and hydrogeology are important considerations for designing subsurface monitoring networks. Often, these networks are used to detect potential releases or characterize existing contamination beneath land-based waste storage facilities. A case study in Santa Barbara, California, U.S.A., illustrates the utility of vadose zone monitoring in characterizing a gasoline contamination problem and guiding the placement of groundwater monitoring wells.     

Simulating Nitrate Leaching Profiles in a Highly Permeable Vadose Zone

An approach is developed to simulate leaching of a dissolved chemical constituent in the vadose zone of an aquifer. Specifically, nitrate loading at the water table for different water table depths, for a range of aquifer permeability values, and for different cases of heterogeneity of the aquifer, are considered. Models from the literature are first used to derive soil–water characteristic curves (water retention and hydraulic conductivity) from a grain size distribution curve for unsaturated conditions. Given infiltration from the surface, the initial conditions for the chemical concentration, and the water content profile, leaching of the chemical in the vadose zone is simulated as a function of both time and depth. The methodology is illustrated for a permeable aquifer. Simulations are undertaken using a finite element code for saturated and unsaturated flow. Different scenarios are simulated depending on the heterogeneity of the aquifer and the depth of the water table. Modeling results show that in the example case studied, nitrate concentration loading at the water table does not depend strongly on the position of the water table, but rather on the material properties of the aquifer. The contribution of this endeavor resides in the methodology which allows a prediction of nitrate leaching using only the grain size property of the aquifer. It allows practitioners to obtain a first assessment of leaching with limited data.     

Natural attenuation of petroleum hydrocarbons—a study of biodegradation effects in groundwater (Vitanovac,Serbia)

The role of natural attenuation processes in groundwater contamination by petroleum hydrocarbons is of intense scientific and practical interest. This study provides insight into the biodegradation effects in groundwater at a site contaminated by kerosene (jet fuel) in 1993 (Vitanovac, Serbia). Total petroleum hydrocarbons (TPH), hydrochemical indicators (O₂, NO₃^?, Mn, Fe, SO₄^2?, HCO₃^?), δ¹³C of dissolved inorganic carbon (DIC), and other parameters were measured to demonstrate biodegradation effects in groundwater at the contaminated site. Due to different biodegradation mechanisms, the zone of the lowest concentrations of electron acceptors and the zone of the highest concentrations of metabolic products of biodegradation overlap. Based on the analysis of redox-sensitive compounds in groundwater samples, redox processes ranged from strictly anoxic (methanogenesis) to oxic (oxygen reduction) within a short distance. The dependence of groundwater redox conditions on the distance from the source of contamination was observed. δ¹³C values of DIC ranged from ??15.83 to ??2.75‰, and the most positive values correspond to the zone under anaerobic and methanogenic conditions. Overall, results obtained provide clear evidence on the effects of natural attenuation processes—the activity of biodegradation mechanisms in field conditions.     

Post-remediation evaluation of a LNAPL site using electrical resistivity imaging

Present understanding of the earth's subsurface is most often derived from samples at discrete points (wells) and interpolations or models that interpret the space between these points. Electrical resistivity imaging techniques have produced an improved capability to map contaminants (especially NAPLs--NonAqueous Phase Liquids) away from traditional wells using actual field data. Electrical resistivity image data, confirmed by drilling, have demonstrated that LNAPL (Light NAPL--less dense than water, such as gasoline) contaminants exist outside of a delineated and remediated area in Golden, Oklahoma. The data also demonstrate that LNAPL exists between monitoring and remediation wells which indicate low contaminant levels when sampled. Additionally, the electrical images provided the drilling location with the highest concentration of hydrocarbon ever found on the site, even after two phases of remediation work had been performed, although the sampling protocols varied. The results indicate that current methods of post-remediation site characterization are inadequate for complete site characterization.     

Modeling the flow and leachate transport in the vadose and saturated zones of a municipal landfill

The purpose of the present study was to evaluate the groundwater contamination due to the construction and operation of the municipal landfill of Amari, Rethymno, Crete. The groundwater flow and leachate transport in the vadose and saturated zones were studied and simulated, using three different models: the one-dimensional groundwater flow and contaminant transport model for the vadose zone Pesticide Root Zone Model (PRZM-3), the Geographical Information System (GIS) Argus ONE and the three-dimensional groundwater flow and contaminant transport model Princeton Transport Code (PTC). The simulation time was 30 and 20 years, and the results obtained, according to the models and the existing hydrogeological conditions, were very encouraging and reassuring about the groundwater quality of the broad region.     

Fate and movement of atrazine, cyanazine, metolachlor and selected degradation products in water resources of the deep Loess Hills of Southwestern Iowa, USA

The environmental fate and movement of herbicides widely used for weed control in corn are assessed for a deep loess soil in southwestern Iowa. Beginning in the early 1980s, the herbicide-based weed control program emphasized the application of atrazine (ATR) or cyanazine (CYN) and metolachlor (MET) for both broadleaf and grass control. Between 1992 and 1995, concentrations of ATR, desethylatrazine (DEA), desisopropylatrazine (DIA), CYN and MET were measured in rainwater, both shallow and deep vadose zone water, and well water. Results show that the frequency of herbicide detections and the range and distribution of occurrences are dependent upon both landscape position and temporal inputs of recharge water from rainfall. Generally, DIA was observed more frequently and in higher mean concentration in well water than DEA, while DEA was observed more frequently than DIA in vadose zone groundwater. A chromatographic analogy is suggested to explain the occurrence patterns observed for both parent herbicide and degradation products within the unsaturated zone water. Analysis of rainwater samples collected during this time also revealed low concentrations of ATR, CYN and MET, with the timing of the detections indicative of non-local transport. Results show that the deep loess soil conducts both water and agricultural chemicals relatively rapidly and as such represents a production system which is vulnerable to contamination of shallow groundwater by herbicide-derived chemicals. Results also illustrate the importance of including major herbicide degradation products in water resource impact assessment studies.     

Geophysical and hydrological data assimilation to monitor water content dynamics in the rocky unsaturated zone

In recent years, geophysics is increasingly used to study the flow and transport processes in the vadose zone. Particularly, when the vadose zone is made up of rocks, it is difficult to install sensors in the subsurface to measure hydrological state variables directly. In these cases, the electrical resistivity tomography (ERT) represents a useful tool to monitor the hydrodynamics of the infiltration and to estimate hydraulic parameters and state variables, such as hydraulic conductivity and water content. We propose an integrated approach aimed at predicting water content dynamics in calcarenite, a sedimentary carbonatic porous rock. The uncoupled hydrogeophysical approach proposed consists in 4D ERT monitoring conducted during an infiltrometer test under falling head conditions. Capacitance probes were installed to measure water content at different depths to validate the estimations derived from ERT. A numerical procedure, based on a data assimilation technique, was accomplished by combining the model (i.e., Richards’ equation) with the observations in order to provide reliable water content estimations. We have used a new data assimilation method that is easy to implement, based on the ensemble Kalman filter coupled with Brownian bridges. This approach is particularly suitable for strongly non-linear models, such as Richards’ equation, in order to take into account both the model uncertainty and the observation errors. The proposed data assimilation approach was tested for the first time on field data. A reasonable agreement was found between observations and predictions confirming the ability of the integrated approach to predict water content dynamics in the rocky subsoil.     

Migration of pollutants in groundwater. VI. Flushing of DNAPL droplets/ganglia

Models for describing the flushing of DNAPL from contaminated aquifers are developed, and the dependence of the calculated cleanup times on the model parameters is explored. Diffusion transport from isolated DNAPL droplets, from low-permeability porous spherical domains containing distributed DNAPL droplets, and from low-permeability porous planar lamellae containing distributed DNAPL is analyzed, and the resulting expressions then coupled with the equations for advective transport of dissolved VOC by means of natural uniform flow and a system of injection and recovery wells generating a two-dimensional flow field. The models are readily run on currently available microcomputers. The results of computations with the models are consistent with the severe tailing and slow rates of remediation which are generally observed when DNAPLs are removed by flushing.     

Using GA-Ridge regression to select hydro-geological parameters influencing groundwater pollution vulnerability

For groundwater conservation and management, it is important to accurately assess groundwater pollution vulnerability. This study proposed an integrated model using ridge regression and a genetic algorithm (GA) to effectively select the major hydro-geological parameters influencing groundwater pollution vulnerability in an aquifer. The GA-Ridge regression method determined that depth to water, net recharge, topography, and the impact of vadose zone media were the hydro-geological parameters that influenced trichloroethene pollution vulnerability in a Korean aquifer. When using these selected hydro-geological parameters, the accuracy was improved for various statistical nonlinear and artificial intelligence (AI) techniques, such as multinomial logistic regression, decision trees, artificial neural networks, and case-based reasoning. These results provide a proof of concept that the GA-Ridge regression is effective at determining influential hydro-geological parameters for the pollution vulnerability of an aquifer, and in turn, improves the AI performance in assessing groundwater pollution vulnerability.     

宁波市环境空气中VOCs污染状况及变化趋势分析

基于近7年来的连续监测数据,对宁波市环境空气中挥发性有机物(VOCs)的污染状况及变化趋势进行了初步分析。研究表明:在宁波市环境空气中检测出94种VOCs,其主要成分是饱和烷烃、芳烃、烯烃、卤代烃、卤代芳烃、含氧有机物等,有37种属有毒有害物质,其中苯系物含量最高;宁波市环境空气中苯系物的污染程度与国内外城市基本处于同一水平,近年来的污染状况变化不大,没有明显恶化;空间分布特征显示一类保护区VOCs的排放以天然源为主,二类各功能区VOCs的排放由天然源和局部人为污染源共同形成,三类区以工业污染源排放为主;时间变化趋势显示VOCs在冬季和春季的平均浓度比其他季节高,VOCs的日变化基本呈现2个主浓度峰值特征,跟城市交通流量变化具有很好相关性。     

Assessing the impact of irrigation treatments on thiram residual trends: Correspondence with numerical modelling and field-scale experiments

The present study was undertaken to study the trends of transport of thiram, a dithiocarbamate pesticide, at different time and depth in the fields under real field conditions for wheat crop. Numerical simulations were carried out by solving the coupled soil–water content movement and mass transport equations using HYDRUS- 1D. The supplementary data used for paramaterization of HYDRUS-1D comprise of irrigation treatments, climatic conditions, and soil characteristics. Results focus on the effects and influence of irrigation treatments on pesticide persistence and mobility. Modelling results were in good agreement with the experimentally determined thiram concentrations. Application of the model to measured field data of thiram movement indicates that the modelling approach can provide reliable and useful estimates of the mass flux of water and non-volatile pesticide in vadose zone. For policy-makers and planners, some regulation strategies are suggested for controlling inappropriate pesticide application under deficit irrigation or rain-fed conditions.     

Application of drastic model and GIS: for assessing vulnerability in hard rock granitic aquifer

Geographic information system (GIS) has become one of the leading tools in the field of hydrogeological science that helps in assessing, monitoring, and conserving groundwater resources. Groundwater is a finite resource, which is being overexploited due to increase in demand over the years leading to decrease in its potentiality. In the present study, DRASTIC model has been used to prepare groundwater vulnerable zone in hard rock aquifer of granitic terrain. The main objective is to determine susceptible zone for groundwater pollution by integrating hydrogeological layers in GIS environment. The layers such as depth of aquifer, recharge, aquifer yield, soil type, topography, vadose zone, and transmissivity are incorporated in the DRASTIC model. The final output of the map shows that around 60% of the area falls under low to no risk of pollution zone. The high risk of pollution zones are mostly present towards the margin of southeastern periphery. The lower part of the basin as well as small area on northern side falls under moderate risk of pollution zone. For the assessment of groundwater pollution zone, 24 groundwater samples have been collected from different vulnerable zones. The chemical analysis of sample shows that the southeastern margin of basin has relatively high concentration of nitrate as compared to other parts of the basin. It is present in high pollution zone as well as moderate pollution zone. The present model can be used for assessment and management of groundwater.     

Beach geomorphic factors for the persistence of subsurface oil from the Exxon Valdez spill in Alaska

Oil from the 1989 Exxon Valdez oil spill persists in some of the Prince William Sound (Alaska) beaches and continues to be a potential threat to the fauna. This paper reports a field investigation during the summer of 2008 of groundwater flow and solute transport in a tidal gravel beach in Smith Island, Prince William Sound. The beach contains oil on one side, the left side (facing landward). Field measurements of water table, salinity, and tracer (lithium) concentration were obtained for an approximate duration of 64 h for two transects, the oiled transect and a clean transect (the right transect). It was found that the hydraulic conductivity and the fresh groundwater recharge into the two transects were similar. It was also found that the beach slope of the mid to high tidal zone along the oiled (left) transect was ~7.4% which is considerably smaller than that of the clean (right) transect (~11.8%). This suggests a higher flushing/replenishing of the right transect with nutrients and/or oxygen, which would have enhanced biodegradation of oil on the right transect if that oil was not washed by waves. We also found that the degree of oiling at each location was inversely dependent on the armoring of the beach surface with clasts and boulders. The applied tracer concentration at the left transect was less than 2% of the source or close to the background level at all locations except a seaward well closest to the applied location, indicating that the tracer applied was diluted or washed out from the beach during the application. Thus, in situations where oil biodegradation is limited by the availability of nutrients and/or dissolved oxygen, applying the chemicals on the beach surface would most likely not enhance oil biodegradation as the applied chemicals would be greatly diluted prior to reaching the oil. Thus, deep injection of nutrients and/or dissolved oxygen is probably the only option for enhancing oil biodegradation.     

常州地区植被排放VOC的估算研究

通过对2011年常州地区各类植物VOC排放因子,以及各类植被分布面积等数据统计分析,采用BEIS模型为参考的估算方法,建立起常州地区植被VOC的排放清单。结果表明,植被所排放VOC的变化规律既与植物本身有关又与气温和太阳辐射有关,区域内年植被VOC的总排放量为1．13×104 t。     

乌鲁木齐河流域浅层地下水防污性能评价

地下水防污性能的评价是确定地下水资源保护措施是否可行的关键。本文根据乌鲁木齐河流域浅层地下水水文地质状况,采用DRASTIC模型,选取包气带岩性、厚度与结构、地形作为评价因子,在乌鲁木齐河流域地下水污染现状评价的基础上,用模糊综合评判法评价了地下水防污性能,从而为乌鲁木齐河流域地下水污染防治提供了依据。     

Corrections for measurements of tritium in subterranean vapor using silica gel

Hazardous contaminants buried within vadose zones can accumulate in soil gas. The concentrations and spatial extent of these contaminants are measured to evaluate potential transport to groundwater for public risk evaluation. Tritium is an important contaminant found and monitored for in vadose zones across numerous sites within the US nuclear weapons complex, including Los Alamos National Laboratory. The extraction, collection, and laboratory analysis of tritium from subterranean soil gas presents numerous technical challenges that have not been fully studied. Particularly, the lack of moisture in the soil gas in the vadose zone makes it difficult to obtain enough sample (e.g., >5 g) to provide for the required measurement sensitivity, and often, only small amounts of moisture can be collected. Further, although silica gel has high affinity for water vapor and is prebaked prior to sampling, there is still sufficient residual moisture in the prebaked gel to dilute the relatively small amount of sampled moisture; thereby, significantly lowering the ??true?? tritium concentration in the soil gas. This paper provides an evaluation of the magnitude of the bias from dilution, provides methods to correct past measurements by applying a correction factor (CF), and evaluates the uncertainty of the CF values. For this, 10,000 Monte Carlo calculations were performed, and distribution parameters of CF values were determined and evaluated. The mean and standard deviation of the distribution of CF values were 1.53 ± 0.36, and the minimum, median, and maximum values were 1.14, 1.43, and 5.27, respectively.     

如何降低水中VOC分析的检测限

环境中挥发性有机污染物（ＶＯＣ）的存在很复杂,随着ＶＯＣ治理的进步,环境水中ＶＯＣ浓度有不断降低的趋势,要求ＶＯＣ分析具有更低的检测限。通过对环境水前处理过程采用优化吹扫捕集条件来扩大试样量,选择高灵敏度的检测器以及降低前处理过程的空白值,提纯分析用水;优化ＶＯＣ色谱分离条件,确保色谱峰良好分离来降低试样和空白值的标准偏差的研究,表明可以有效降低水中ＶＯＣ分析方法的检测限。     

The Emissions of Major Aromatic Voc as Landfill Gas from Urban Landfill Sites in Korea

In this study, concentrations of major aromatic VOCs were determined from landfill gas (LFG) at a total of five municipal landfill sites in Korea including Nan Ji (NJ), Woon Jung (WJ), Sam Poong (SP), Hoei Chun (HC), and No Hyung (NH). The concentration levels of those VOC were found to be significantly different, mainly as a function of such a parameter as landfill aging. The VOC concentrations measured from the unclosed landfill sites (e.g., WJ) were characterized by exceedingly high values above a few tens of ppm. However, the results of the abandoned site (e.g., SP) were about three orders of magnitude lower than the others so as to merely exceed the typical ambient concentration levels. It was most striking to find a systematic dominance of toluene over other aromatic VOC under most circumstances. The LFG flux values of all aromatic VOC and the four specific major ones (termed as BTEX: benzene, toluene, ethylbenzene, and xylene) were also computed for each vent pipe from all study sites using their concentrations and the concurrently determined environmental parameters. The results, if calculated in terms of the average BTEX quantity emitted per vent pipe, showed that the magnitude of their emissions can vary substantially, with the values ranging from 0.05 (SP) to 49.2 kg yr⁻¹ (WJ in wintertime). The LFG flux values of aromatic VOC, when compared to the contribution of non-methane hydrocarbons (NMHC), were able to explain a constant, but minor, proportion of the LFG carbon budget.     

Contamination Levels and Preliminary Assessment of the Technical Feasibility of Employing Natural Attenuation in 5 Priority Areas of Presidente Bernardes Refinery in Cubatão, São Paulo, Brazil

Five priority areas of potential impact by contaminants (API) were investigated at the Presidente Bernardes Refinery in Cubatão, São Paulo, Brazil with the following aims: (i) to identify both organic and inorganic contaminants present in soil and groundwater; (ii) to define the environmental conditions relevant for microbial activity at the site and (iii) to evaluate the feasibility of employing natural attenuation for treatment of the hydrocarbon contamination. One area (API 1) was an uncontrolled landfill, where waste materials from the refinery were deposited between 1954 and 1986, and four areas (API 4, 5, 7 and 11) were located in the operational section of the refinery. Soil contamination by regulated BTEX compounds (benzene, toluene, total xylenes) was restricted to two samples from API 1. Nonregulated ethylbenzene was detected in one soil sample from API 4, one from API 5 and two from API 1. No soil contained regulated PAH above threshold levels. Several nonregulated PAHs were found in 6 soil samples from API 1, 3 soil samples from API 4 and 1 soil sample from API 5. Site soils contained very high aluminium concentrations, but metal contamination was restricted to one soil sample from API 1, which contained nickel above threshold limits. BTEX contamination of groundwater was due mostly to benzene. Of the 17 PAH molecules tested, only naphthalene and 2-methylnaphthalene occurred in groundwater. The sum of total BTEX and total PAH exceeded 200 μg/L in only a few monitoring wells in API 4, 5 and 11 and was always below 2.640 μg/L. Be, Cd, Cr, Cu, Hg, Ni, Se, Ag, Tl and Zn were not detected in groundwater, which was contaminated in a few locations by aluminium (mostly below 1 mg/L), lead (<0.066 mg/L) and arsenic (<0.056 mg/L). S, K, Ca, Mg and Fe were present in groundwater in excess of physiological requirements for microbial growth, but low concentrations of N and P could become growth limiting. However, BTEX were efficiently degraded in saturated and unsaturated zone microcosms and nutrient amendments did not stimulate biodegradation rates measurably. The inorganic carbon pool in groundwater was up to one order of magnitude larger than the organic carbon pool. Total inorganic carbon (TIC) in API groundwater exceeded TIC of clean groundwater by factors of 2 (API 4), 6 (API 5, 7 and 11) or 10 (API 1). Most of the inorganic carbon incorporated into groundwater beneath the refinery originated from biodegradation in the unsaturated soil, which contained a microbiota (10⁶ cells/g on average) capable of growth with most of the pure (benzene, toluene, ethylbenzene and xylene) and mixed hydrocarbons tested (diesel oil, gasoline, naphtha, condensate, aromatic residue and fuel oil). A viscous hydrocarbon paste uncovered in API 1 was insoluble in water but dissolved in dichloromethane. Many organic components of this paste were biodegradable as evidenced by weight reduction of the hydrocarbon paste and by the growth of suspended and attached biomass in saturated zone microcosms, where the paste was the only carbon source. This study indicates that monitored natural attenuation may be a technically feasible and efficient means for plume control in API 1, 4 and 5, provided the plumes in API 4 and 5 are not expanding. This technique is not suitable for contaminant reduction in API 11.