Surface catalyzed Fenton treatment of bis(2-chloroethyl) ether and bis(2-chloroethoxy) methane

This study examined the feasibility of using surface catalyzed Fenton treatment to remediate soil and groundwater contaminated by the chlorinated ethers, bis(2-chloroethyl) ether (BCEE) and bis(2-chloroethoxy) methane (BCEM). Parameters that affect the contaminant loss rate such as porewater pH, hydrogen peroxide concentration, and solid/water ratio were systematically evaluated. Batch reactors were set-up utilizing either contaminated or uncontaminated soil, obtained from an industrial site in Moss Point, MS, that was mixed with synthetic groundwater containing the contaminants of interest. The results show an increase in contaminant reduction with a decrease in pH, an increase in hydrogen peroxide concentration, or an increase in the solid/water ratio. For a similar set of conditions, contaminant reduction was greater for systems utilizing contaminated soil as compared to the systems containing uncontaminated soil. In addition, specific oxygen uptake rates (SOURs) were measured for biomass, collected from an activated sludge plant, exposed to different dilutions of untreated and surface catalyzed Fenton treated water to evaluate whether residual BCEE, BCEM, and their co-contaminants as well as their oxidation by-products were potentially inhibitory or can potentially serve as a substrate for the biomass. The measured SOURs show that the surface catalyzed Fenton treatment enhanced the biodegradability of the contaminated groundwater and served as a substrate for the biomass.     

Environmental monitoring in the Mar Grande basin (Ionian Sea,Southern Italy)

Hydrodynamic and water quality data has been recorded since February 2014 by a meteo-oceanographic station installed in the inner part of the Gulf of Taranto, in the northeastern part of the Ionian Sea (Southern Italy). This monitoring action, managed by the research unit of the Technical University of Bari, DICATECh Department, could play a pivotal role in a vulnerable and sensitive area, affected by massive chemical and biological pollutant discharges due to the presence of heavy industry and intense maritime traffic. Monthly trends of winds, waves, currents, and biochemical parameters, such as dissolved oxygen, chlorophyll, and turbidity, are analyzed and discussed. The analysis exhibits that the wave regime is slightly controlled by wind forcing; rather, topography strongly affects the wave propagation direction. Surface currents appear wind induced in the measuring station, while near the bottom a quasi-steady current directed towards southwest is formed. The selected water quality indicators show monthly trends consistent with the typical seasonal convective fluxes and mixing.     

Sorption and desorption of diuron on Typic Argiudoll,Oxic Argiudoll and on their clay fractions: environmental aspects

Abstract

The sorption and desorption of diuron by soil samples from Horizons A and B (HA and HB) and by their different clay fractions were investigated, using two soil samples, classified as Typic Argiudoll and Oxic Argiudoll. The sorption and desorption curves were adjusted to the Freundlich model and evaluated by parameters K_f, K_d and K_oc. Based on the data of groundwater ubiquity score (GUS), leachability index (LIX) and hysteresis index (HI), the risk of groundwater pollution was evaluated. The K_d values obtained for soil samples were between 4.5?mL g^?1 (Oxic Argiudoll – HB) and 15.9?mL g^?1 (Typic Argiudoll – HA) and between 1.13 and 14.0?mL g^?1 for the different mineral fractions, whereas the K_oc values varied between 276 (Oxic Argiudoll – HB) and 462 (Typic Argiudoll – HA). According to the parameter GUS, only Oxic Argiudoll – HB presented leaching potential, and based on the LIX index this same soil presented the highest leaching potential. Some samples presented low LIX and GUS values, indicating no leaching potential, but none presented HI results indicative of hysteresis, suggesting weak bonds between diuron and the soil samples and, hence, the risk of groundwater pollution by diuron.     

An interprovincial cooperative game model for air pollution control in China

The noncooperative air pollution reduction model (NCRM) that is currently adopted in China to manage air pollution reduction of each individual province has inherent drawbacks. In this paper, we propose a cooperative air pollution reduction game model (CRM) that consists of two parts: (1) an optimization model that calculates the optimal pollution reduction quantity for each participating province to meet the joint pollution reduction goal; and (2) a model that distribute the economic benefit of the cooperation (i.e., pollution reduction cost saving) among the provinces in the cooperation based on the Shapley value method. We applied the CRM to the case of SO₂ reduction in the Beijing–Tianjin–Hebei region in China. The results, based on the data from 2003–2009, show that cooperation helps lower the overall SO₂ pollution reduction cost from 4.58% to 11.29%. Distributed across the participating provinces, such a cost saving from interprovincial cooperation brings significant benefits to each local government and stimulates them for further cooperation in pollution reduction. Finally, sensitivity analysis is performed using the year 2009 data to test the parameters’ effects on the pollution reduction cost savings.

Implications: China is increasingly facing unprecedented pressure for immediate air pollution control. The current air pollution reduction policy does not allow cooperation and is less efficient. In this paper we developed a cooperative air pollution reduction game model that consists of two parts: (1) an optimization model that calculates the optimal pollution reduction quantity for each participating province to meet the joint pollution reduction goal; and (2) a model that distributes the cooperation gains (i.e., cost reduction) among the provinces in the cooperation based on the Shapley value method. The empirical case shows that such a model can help improve efficiency in air pollution reduction. The result of the model can serve as a reference for Chinese government pollution reduction policy design.     

The groundwater contribution to surface water contamination in a region with intensive agricultural land use (Noord-Brabant, The Netherlands)

Traditionally, monitoring of soil, groundwater and surface water quality is coordinated by different authorities in the Netherlands. Nowadays, the European Water Framework Directive (EU, 2,000) stimulates an integrated approach of the complete soil-groundwater-surface water system. Based on water quality data from several test catchments, we propose a conceptual model stating that stream water quality at different discharges is the result of different mixing ratios of groundwater from different depths. This concept is used for a regional study of the groundwater contribution to surface water contamination in the Dutch province of Noord-Brabant, using the large amount of available data from the regional monitoring networks. The results show that groundwater is a dominant source of surface water contamination. The poor chemical condition of upper and shallow groundwater leads to exceedance of the quality standards in receiving surface waters, especially during quick flow periods.     

Mercury baseline levels in Flemish soils (Belgium)

It is important to establish contaminant levels that are normally present in soils to provide baseline data for pollution studies. Mercury is a toxic element of concern. This study was aimed at assessing baseline mercury levels in soils in Flanders. In a previous study, mercury contents in soils in Oost-Vlaanderen were found to be significantly above levels reported elsewhere. For the current study, observations were extended over two more provinces, West-Vlaanderen and Antwerpen. Ranges of soil Hg contents were distinctly higher in the province Oost-Vlaanderen (interquartile range from 0.09 to 0.43 mg/kg) than in the other provinces (interquartile ranges from 0.7 to 0.13 and 0.7 to 0.15 mg/kg for West-Vlaanderen and Antwerpen, respectively). The standard threshold method was applied to separate soils containing baseline levels of Hg from the data. Baseline concentrations for Hg were characterised by a median of 0.10mg Hg/kg dry soil, an interquartile range from 0.07 to 0.14 mg/kg and a 90% percentile value of 0.30 mg/kg. The influence of soil properties such as clay and organic carbon contents, and pH on baseline Hg concentrations was not important. Maps of the spatial distribution of Hg levels showed that the province Oost-Vlaanderen exhibited zones with systematically higher Hg soil contents. This may be related to the former presence of many small-scale industries employing mercury in that region.     

Evaluation of groundwater contamination in a coastal area of south-eastern Sicily

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides…) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO?2?), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells.     

The ratio of clay content to total organic carbon content is a useful parameter to predict adsorption of the herbicide butachlor in soils

Thirteen soils collected from 11 provinces in eastern China were used to investigate the butachlor adsorption. The results indicated that the total organic carbon (TOC) content, clay content, amorphous Fe2O3 content, silt content, CEC, and pH had a combined effect on the butachlor sorption on soil. Combination of the data obtained from the 13 soils in the present study with other 23 soil samples reported by other researchers in the literature showed that Koc would be a poor predictive parameter for butachlor adsorption on soils with TOC content higher than 4.0% and lower than 0.2%. The soils with the ratio of clay content to TOC content (RCO) values less than 60 adsorbed butachlor mainly by the partition into soil organic matter matrix. The soils with RCO values higher than 60 apparently adsorbed butachlor by the combination of the partition into soil organic matter matrix and adsorption on clay surface.     

Source and release mechanism of arsenic in aquifers of the Mekong Delta, Vietnam

In order to elucidate the arsenic source and its release mechanism into groundwater in the Mekong Delta, Vietnam, groundwater samples were collected from wells at different depths (20 to 440 m) and core samples (from 20 to 265 m depth) were analyzed. Based on the analytical results for groundwater and core samples, the As source in groundwater is considered to be pyrite (FeS(2)) in acid sulfate soil (ASS) under oxidizing conditions and hydrous ferric oxide (Fe(OH)(3)) under reducing conditions. Geochemical modeling demonstrated that As(III) is the dominant species and the presence of As-bearing sulfides, Fe-bearing sulfides and oxides phases may locally act as potential sinks for As. From variation between Fe and As concentrations in groundwater samples, the release mechanism of As is: dissolution of Fe(OH)(3) containing As under reducing conditions and oxidative decomposition of FeS(2) containing As under oxidizing conditions.     

Seasonal variation and factors influencing perchlorate in water,snow, soil and corns in Northeastern China

Seasonal variation and influencing factors of perchlorate in snow, surface soil, rain, surface water, groundwater and corn were studied. Seven hundreds and seventy samples were collected in different periods in Harbin and its vicinity, China. Perchlorate concentrations were analyzed by ion chromatography–electrospray mass spectrometry. Results indicate that fireworks and firecrackers display from the Spring Festival to the Lantern Festival (February 2, 2011–February 17, 2011) can result in the occurrence of perchlorate in surface soil and snow. Perchlorate distribution is affected by wind direction in winter. Melting snow which contained perchlorate can dissolve perchlorate in surface soil, and then perchlorate can percolate into groundwater so that perchlorate concentrations in groundwater increased in spring. Perchlorate concentrations in groundwater and surface water decrease after rainy season in summer. Groundwater samples collected in the floodplain areas of the Songhua River and the Ashi River contained higher perchlorate concentrations than that far away with the rivers. The corns have the ability to accumulate perchlorate.     

关中清灌区农田生态系统污染现状研究

对陕西关中地区清灌区土壤、粮食、地下水及农田退水中的重金属、含氮化合物等污染物进行了分析研究,结果表明：灌区土壤重金属含量在陕西土壤背景值范围内,主要粮食作物尚未受到污染（除F外）,但地下水已受到重金属、含氮化合物的污染。同时,灌区农田退水中三氮含量较高,直接排放渭河水体后,影响了渭河水质。另外还发现灌溉能减低土壤F污染。     

Reduction of nitrobenzene in groundwater by iron nanoparticles immobilized in PEG/nylon membrane

The highly reactive iron nanoparticles (NPs) immobilized in nylon membrane were synthesized and characterized, and the reduction of nitrobenzene (NB) in groundwater by the NPs was investigated. Environmental scanning electron microscopy (ESEM) images showed that the NPs distributed homogeneously on the membrane surface without agglomeration. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the NPs immobilized in membrane were mainly composed of Fe-oxides rather than zero-valent iron. Thermogravimetric (TG) analysis suggested that the weight percentage of the immobilized NPs and the oxygen introduced to the reacted sample after 80min reaction were about 18.5% and 13%, respectively. Moreover, Fourier transform infrared (FTIR) analysis further demonstrated the changes on the membrane surface after thermal grafting, NPs immobilizing and reacting for 80min. Using the reactive NPs immobilized in nylon membrane, NB in groundwater was rapidly and quantitatively decreased by 68.9% just in the first 20min, the Fe(2+) associated with the iron NPs immobilized in PEG/nylon66 membrane was mainly responsible for this reduction. The reaction appeared to follow pseudo-first-order kinetics and the rate constants increased upon decreasing the pH value. The samples we prepared exhibited good corrosion resistance for humic acid (HA) but had a short-term performance for NB degradation. More so, the groundwater chemistry had a negative influence on the reactivity of membrane immobilized NPs.     

Monitoring of PCDD/Fs and dioxin-like PCBs and seasonal variations in mussels from the Mar Grande and the Mar Piccolo of Taranto (Ionian Sea,Southern Italy)

The levels and specific profiles of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in Mytilus galloprovincialis from the Mar Grande and the Mar Piccolo of Taranto were determined during the extensive monitoring plan of Local Health Authority to assess PCDD/Fs and DL-PCBs contamination in food and farm products, within 20 km from the industrial areas of Taranto, between March and December 2011. The average Total Toxicity Equivalence (TEQ) values for the sum of PCDD/F and DL-PCBs ranged from 1.61 to 5.63 pg WHO₂₀₀₅-TEQ g^?1 wet weight basis, with the highest in the first inlet of the Mar Piccolo. In particular, DL-PCBs were the dominant chemicals in all samples, followed by PCDFs and PCDDs. Congener patterns in mussels were similar, indicating a homogeneous behavior in studied areas and, probably, the same type of source. The seasonal concentrations trend showed a relevant increase of dioxin and dioxin-like PCBs TEQs during the summer months, exceeding the limits set by the European Community for food and foodstuff. Reducing PCDD/Fs and PCBs is necessary to decrease contamination levels in order to safeguard marine ecosystem and human health in the Taranto area.     

Review of concentrations and chemistry of trichloroacetate in the environment

This paper reviews the concentrations of trichloroacetate (TCA) in the atmosphere-plant-soil system. Data originate mainly from Europe. The median TCA concentration in rainwater and canopy drip decreased until 1995. From then the median TCA concentration in rainwater remains rather constant while for canopy drip later data are not available. The same seems to hold for concentrations in air although a very limited data set is available. The median concentrations in coniferous needles and groundwater are constant for the period observed. The median TCA concentrations in soil decreased until 1992 and then remained constant.The TCA formation from chlorinated solvents in the atmosphere may explain a substantial percentage of the TCA amount in the atmosphere. The TCA concentrations in rainwater and canopy drip indicate that there will be other sources contributing to 10-50%. Waste incineration, biomass burning and natural formation in the marine boundary layer are potential candidate sources of TCA, but nothing can be said as yet on their TCA emission rates. Anthropogenic emissions of chlorine could also be a source.TCA can be formed from chlorinated solvents by biota. However, for coniferous trees the uptake of TCA from soil may be the predominant route. Biotic and abiotic reactions can cause to formation of TCA in soil, but also formation of TCA from chlorinated solvents by biota that excrete TCA, may contribute. Mass balance calculations of the bioactive soil top layer show that the production rate of TCA in certain soil types could be substantial. The mass balance calculations could not distinguish between natural and anthropogenic sources in soil.     

Analysis of munitions constituents in groundwater using a field-portable GC-MS

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory’s turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples.The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ∼1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.     

LC-MS/MS method validation for determination of selected neonicotinoids in groundwater for the purpose of a column experiment

The work was carried out to develop and validate a method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for the simultaneous detection and quantification of five neonicotinoid insecticides: acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam in groundwater samples for the purpose of a further column experiment. This experiment will be used to analyze breakthrough curves of neonicotinoids under a saturated water flow to set transport parameters, where the reliability of the results of chemical analysis plays an important role. The validation was performed in a concentration range from 0.09?µg L^?1 to 100?µg L^?1 using an Infinity 1290 (Agilent, USA) chromatograph coupled with a QTrap 5500 mass spectrometer (Sciex, Canada). The calibration curves were obtained on the basis of the results of six standard solution analyses. Linearity was not lower than 0.998. The limit of detection was set at the lowest concentration which can be determined with an acceptable accuracy and precision. All pesticides had recoveries in the range 85–109% with relative standard deviation values less than 8.1%. The estimated measurement uncertainty did not exceed 30%, so the LC-MS/MS method fits for the intended purpose.     

The dynamics of arsenic in four paddy fields in the Bengal delta

Irrigation with arsenic contaminated groundwater in the Bengal Delta may lead to As accumulation in the soil and rice grain. The dynamics of As concentration and speciation in paddy fields during dry season (boro) rice cultivation were investigated at 4 sites in Bangladesh and West Bengal, India. Three sites which were irrigated with high As groundwater had elevated As concentrations in the soils, showing a significant gradient from the irrigation inlet across the field. Arsenic concentration and speciation in soil pore water varied temporally and spatially; higher As concentrations were associated with an increasing percentage of arsenite, indicating a reductive mobilization. Concentrations of As in rice grain varied by 2-7 fold within individual fields and were poorly related with the soil As concentration. A field site employing alternating flooded-dry irrigation produced the lowest range of grain As concentration, suggesting a lower soil As availability caused by periodic aerobic conditions.     

Degradation and leaching of the herbicides metolachlor and diuron: a case study in an area of Northern Italy

In this work the degradation of the herbicides metolachlor, diuron, monuron and of the metabolites 2-ethyl-6-methylaniline (EMA), and 3,4-dichloroaniline (DCA) was assessed in laboratory experiments on microbiologically active and sterilized soils. Their leaching potentials were calculated, using Gustafson's equation, by determining their mobility (as Koc) and persistence (expressed as DT50). Lysimeter experiments were also conducted to assess the actual leaching of the studied herbicides in a cereal crop tillage area vulnerable to groundwater contamination. The data obtained from the field were compared to the laboratory results. Moreover, some compounds of particular concern were searched for in the groundwater located near the experimental area in order to evaluate actual contamination and to test the reliability of the leaching potential. The GUS index, computed on data from microbiologically active soil, shows monuron as a leacher compound, EMA and DCA as non-leachers, metolachlor and diuron as transient ones. The presence of metolachlor in the groundwater monitored, even at concentrations up to 0.1 mug/l, confirms the possibility that transient compounds can be leached if microbial activity has not completely occurred in active surface soil.     

Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils

The transport and fate of the pharmaceutical carbamazepine (CBZ) were investigated in the Dan Region Reclamation Project (SHAFDAN), Tel-Aviv, Israel. Soil samples were taken from seven subsections of soil profiles (150 cm) in infiltration basins of a soil aquifer treatment (SAT) system. The transport characteristics were studied from the release dynamics of soil-resident CBZ and, subsequently, from applying a pulse input of wastewater containing CBZ. In addition, a monitoring study was performed to evaluate the fate of CBZ after the SAT. Results of this study indicate adsorption, and consequently retardation, in CBZ transport through the top soil layer (0-5 cm) and to a lesser extent in the second layer (5-25 cm), but not in deeper soil layers (25-150 cm). The soluble and adsorbed fractions of CBZ obtained from the two upper soil layers comprised 45% of the total CBZ content in the entire soil profile. This behavior correlated to the higher organic matter content observed in the upper soil layers (0-25 cm). It is therefore deduced that when accounting for the full flow path of CBZ through the vadose zone to the groundwater region, the overall transport of CBZ in the SAT system is essentially conservative. The monitoring study revealed that the average concentration of CBZ decreased from 1094 ± 166 ng L⁻¹ in the recharged wastewater to 560 ± 175 ng L⁻¹ after the SAT. This reduction is explained by dilution of the recharged wastewater with resident groundwater, which may occur as it flows to active reclamation wells.     

Treatability of nonylphenol ethoxylate surfactants in on-site wastewater disposal systems.

The fate of nine-mole nonylphenol ethoxylate (NPE9) discharged to an on-site wastewater disposal (septic) system was the focus of a 2-year investigation. Known amounts of NPE9-based detergent were metered daily into the plumbing at a single-family household. The ethoxylate-containing wastewater was discharged to the highly anoxic environment of a 4500-L septic tank before distribution to the oxic subsurface via 100 m of leach line. After 180 days of injecting detergent to the septic system, periodic soil pore water and/or groundwater samples were collected and analyzed for nonylphenol ethoxylates (NPEs), nonylphenol ether carboxylates, and nonylphenol. The NPE9 and degradation intermediates that were measured were reduced by 99.99% on a molar basis. An 18% reduction in molar concentration within the septic tank was observed. This was followed by a further 96.7% reduction of molar concentration within the leach lines. As the pore water migrated through the vadose zone, an additional 99.69% reduction in molar concentration was measured between the bottom of the leach lines (leach line effluent) and the lowest vadose zone monitoring location. The results obtained from these analyses indicate that degradation of the surfactant occurs within the anoxic portion of the disposal system with continued rapid biodegradation in the oxic unsaturated zone. Only trace amounts of degradation residuals were detected in soil pore water. The concentration and distribution of various degradation intermediates with respect to location, time, and ambient physical conditions were evaluated. Rapid and systematic degradation of NPE in on-site wastewater disposal systems was documented.