Treatment of metal-chloride-enriched wastewater by simulated constructed wetlands

The ability of surface flow and subsurface flow simulated wetlands to remove heavy metals from a NaCI-enriched wastewater was examined, employing bulrush (Scirpus validus) and cattail (Typha angustifolia) plants, and two organically amended substrates (mixtures of mushroom compost and leaf litter,with topsoil) with a limestone liner. A simulated wastewater solution containing Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn as chloride salts was added to the wetlands at a rate of 0.3 l h^–1. During 12 weeks of surface flow, Fe was retained most efficiently (74%), and Mn the least (24%). Most metal retention occurred in residual forms, primarily in the upper 5 cm of the substrate. A subsequent 10 week subsurface flow treatment exhibited greater removal efficiencies for all metals, probably due to increased contact with the highly buffered lower substrate. During both treatments, bioaccumulation occurred in plants, but accounted for a very small portion of the total metal removal. Plant species did not significantly influence wetland performance with respect to metal retention. Substrate type did not affect removal efficiency for most metals, but did influence the forms of the metals retained in the wetland.To whom correspondence should be addressed.     

Colloid‐facilitated transport of metolachlor through intact soil columns

Abstract

This study evaluated the role of water dispersible colloids with diverse physicochemical and mineralogical characteristics in facilitating the transport of metolachlor through macropores of intact soil columns. The soil columns represented upper solum horizons of an Alfisol in the Bluegrass region of Kentucky. Three different colloid suspensions tagged with metolachlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide] were introduced at a constant flux into undisturbed soil columns. The eluents were collected and analyzed periodically for colloid and metolachlor concentrations. Colloid recovery in the eluents ranged from 54 to 90 %. The presence of colloids enhanced the transport of metolachlor by 22 to 70 % depending on the colloid type and mobility. Colloids with higher pH, organic carbon, cation exchange capacity (CEC), total exchangeable bases (TEB), surface area (SA), and electrophoretic mobility (EM), showed better mobility, greater affinity for interaction with the herbicide and, thus, greater potential to co‐transport metolachlor. In contrast, increased level of kaolinite, Fe, and Al inhibited metolachlor adsorption and transport. In spite of the increased transportability of metolachlor by the presence of soil colloids, the colloid bound herbicide portion accounted for a very small part of the observed increase. This suggests that surface site exclusion mechanisms and preferential sorption induced by the presence of colloids are more important than ion exchange phenomena in promoting herbicide mobility in subsurface environments.     

Constructed wetlands treating highway runoff in the central Mediterranean region

Two free water surface (FWS) and two subsurface flow (SSF) pilot-size constructed wetlands treating highway runoff (HRO) were monitored over a period of two years (September 2005-August 2007). One FWS and one SSF were designed with a hydraulic retention time (HRT) of 12h, named FWS12 and SSF12, respectively, with each one capable of treating a maximum HRO of 12.6 m(3) d(-1). The other couple, named FWS24 and SSF24, respectively, was designed with an HRT of 24h, with each receiving a maximum HRO of 6.3 m(3) d(-1). The influent flowed from a highway section with a total surface 2752 m(2) on the island of Crete, Greece, in the heart of the South-Central Mediterranean region. Influent and effluent were monitored for COD, TSS, total N (TN), NO(3)(-) and total P (TP) concentrations. Furthermore, removal efficiencies were examined for heavy metals (Cu, Ni, Pb, Zn) for both years, while polycyclic aromatic compounds (PAHs) were examined for the period between September 2006 and August 2007. The influent had a two-year average COD value of 101 mg l(-1), whereas the mean values for TSS, TN, N-NO(3)(-) and TP were 203, 4.30, 1.25 and 4.17 mg l(-1), respectively. For Cu, Ni, Pb and Zn the respective two-year mean influent concentrations were 56, 114, 49 and 250 microg l(-1). Mean concentration of total PAHs in runoff (summation operator PAHs, 16 compounds) were 12.01 microg l(-1). The performance among the four beds was not significantly different according to ANOVA analysis followed by Tukey test (at p<0.05) for almost all the above physicochemical parameters, suggesting that all systems performed in a similar way. All studied systems, achieved a mean of two-year removal efficiencies of 47% for COD, 89% for TSS, 49% for TN, 58% for N-NO(3)(-), 60% for TP, 47% for Cu, 23% for Ni, 33% for Pb, 61% for Zn and 59% for summation operator PAHs (16 compounds).     

Volatile Organic Compounds Selection for Incorporation in Photochemical Mechanisms and the Development of Secondary Pollution Reduction Strategies

In the present work a method for the evaluation of the importance of the VOCs species is presented, aiming to provide criteria for the incorporation of these species into atmospheric photochemical mechanisms and for the successful application of secondary pollution reduction strategies. According to the method presented here, the species can be divided into more important and less important ones, taking into account their mixing ratios and emission values in combination with their reactivity. For this classification three quantitative and one qualitative criteria were introduced. Overall, it is concluded that alkenes with more than a few carbon atoms in their chain appear to be more important in urban and suburban areas, while in background conditions the alkanes, having the smaller chain (ethane, propane), become more important. In the case of alkenes there is no clear species classification, except for the biogenically emitted compounds, isoprene and limonene. In general, more important alkenes appear to be those with the smaller chain (ethene, propene, butene). Most abundant aromatics are benzene, toluene, and xylene. In background conditions higher aromatics are also important, especially 1,2,3-, 1,3,5-, and 1,2,4-trimethylbenzene. The most important carbonylic compounds are formaldehyde, acetaldehyde, and acetone. Finally, taking into account the results mentioned above, a new photochemical mechanism was developed. The species and species groups used in the proposed mechanism are: ethane, higher alkanes, ethene, propene, 2- butene, 1-alkenes, 2-alkenes, higher alkenes, benzene, toluene, m-, o-, p-xylene, 1,3,5-, 1,2,3-, 1,2,4-trimethylbenzene, higher aromatics, formaldehyde, acetaldehyde, higher aldehydes, isoprene, limonene, and other biogenic VOCs.     

Construction Simplicity and Cost as Selection Criteria Between Two Types of Constructed Wetlands Treating Highway Runoff

Two free water surface (FWS) and two subsurface flow (SSF) pilot-size wetlands were constructed for the evaluation of their performance in treating highway runoff (HRO) in the heart of the Mediterranean region, the island of Crete, at the southernmost point of Greece. Detailed recordings of the resources involved during the construction allowed a thorough calculation of the cost of the systems and the requirements in materials, man-hours, and equipment. The two identical FWS systems had a surface area of 33 m² each, while the two identical SSF covered 32 m² each. One FWS and one SSF, named FWS12 and SSF12, respectively, were designed with a hydraulic retention time (HRT) of 12 h, with each one capable of treating a maximum HRO of 12.6 m³/day. The other couple, named FWS24 and SSF24, respectively, was designed with an HRT of 24 h, with each receiving a maximum HRO of 6.3 m³/days. An influent storage tank was required to hold the runoff during the common storm events and control the flow rate (and the hydraulic retention time) into the wetlands. This construction represented 25% of the total construction cost, while 5% was spent on the influent automated (and sun-powered) control and distribution system, from the storage tank to the wetlands. The respective total cost allocated to the two SSF systems (€14,676) was approximately 10% higher than that of the FWS (€13,596), mainly due to the three different-sized gravel layers used in the SSF substrate compared to the topsoil used in the FWS, which tripled the cost and placement time. The Total Annual Economic Cost (TAEC) was €1799/year and €1847/year for the FWS and SSF pair, respectively. TAEC was also used to compare the economic efficiency of the systems per cubic meter of HRO treated and kilograms of COD and TSS removed from the wetlands during their first operational year. Based on these estimations, FWS12 recorded the lowest TAEC_COD and TAEC_TSS values (€89.09/kg and €43.69/kg, respectively) compared to the other three systems, presenting a more economically favorable option.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

PM10 regional transport pathways in Thessaloniki,Greece

In this study, the most dominant regional transport pathways for the city of Thessaloniki, Greece were identified and linked to air quality issues with respect to particulate matter (PM). Using air mass trajectories, cluster analysis techniques and PM10 measurements of a background-urban station of the greater Thessaloniki area during 2001–2004, it was found that north-eastern and southern flows were the most frequent in appearance with high potential to influence the city of Thessaloniki, especially when coinciding with biomass burning or Saharan dust events correspondingly. These incidents appeared to occur mostly during summer adding to a PM10 monthly mean up to 10 μg m^?3. High concentrations of surface PM10 related to north-eastern flows were in most cases accompanied with high aerosol columnar optical depths implying that particulate matter transport from the North-East was multi-layered. South-southwesterly flows originating from N. Africa, though less frequent, seemed to affect decisively Thessaloniki's aerosol budget especially during transition seasons. These flows were related with an increase of the monthly PM10 average up to 20–30 μg m^?3 for the time period studied. Finally, northerly flows were found to transport rather clean air masses that did not seem to contribute to the air quality deterioration of the city.     

Biosolid colloid-mediated transport of copper, zinc, and lead in waste-amended soils

Increasing land applications of biosolid wastes as soil amendments have raised concerns about potential toxic effects of associated metals on the environment. This study investigated the ability of biosolid colloids to transport metals associated with organic waste amendments through subsurface soil environments with leaching experiments involving undisturbed soil monoliths. Biosolid colloids were fractionated from a lime-stabilized, an aerobically digested, and a poultry manure organic waste and applied onto the monoliths at a rate of 0.7 cm/h. Eluents were monitored for Cu, Zn, Pb, and colloid concentrations over 16 to 24 pore volumes of leaching. Mass-balance calculations indicated significantly higher (up to 77 times) metal elutions in association with the biosolid colloids in both total and soluble fractions over the control treatments. Eluted metal loads varied with metal, colloid, and soil type, following the sequences Zn = Cu > Pb, and ADB > PMB > LSB colloids. Colloid and metal elution was enhanced by decreasing pH and colloid size, and increasing soil macroporosity and organic matter content. Breakthrough curves were mostly irregular, showing several maxima and minima as a result of preferential macropore flow and multiple clogging and flushing cycles. Soil- and colloid-metal sorption affinities were not reliable predictors of metal attenuation/elution loads, underscoring the dynamic nature of transport processes. The findings demonstrate the important role of biosolid colloids as contaminant carriers and the significant risk they pose, if unaccounted, for soil and ground water contamination in areas receiving heavy applications of biosolid waste amendments.     

PLATE JUNCTIONS AND HYDROCARBON ACCUMULATIONS IN THE INDIAN REGION

This article relates the productive and potential oil fields in India to plate junctions and other major tectonic features. High geothermal gradients are known to accelerate the expulsion of petroleum from the source bed, as well as its migration and accumulation in favourable reservoir rocks, resulting in high yield. Some of the world's major petroleum deposits occur along ‘failed arms’ associated with the plume generated triple junctions. Seven triple junctions have been located in the Indian region, and two more are identified here. Interestingly, India's off-shore petroleum prospects coincide with some of these triple junctions. Cet article établit la relation entre les champs de pétrole en production et potentiels en Inde à la théorie des plaques et à d'autres traits tectoniques importants. L'on sait que des gradients géothermiques élevés accélèrent l'expulsion du pétrole à partir de la roche-mère et favorisent la migration et l'accumulation dans des réservoirs convenables. Quelques-uns des plus grands champs de pétrole du monde se rencontrent en liaison avec des ‘bras morts’ associés avec un système triple de fossés d'effondrement. Sept systèmes triples ont été repérés en Inde et deux autres sont reconnus ici. II est intéressant de remarquer que les possibilités pétrolières de l'offshore indien coïncide avec certains de ces systèmes triples. Este artículo establece la relación entre los campos petrolíferos en producción y potenciales de India a la teoría de placas y otros aspectos tectónicos. Es sabido que una gradiente térmica alta ascelera la expulsión del petróleo desde la roca madre y favorece su migración y acumulación en rocas reservorio favorables. Algunos de los mayores depósitos de petróleo se encuentran a lo largo de los “brazos muertos” asociados a un sistema triple de unión de placas. Siete uniones de este tipo habia sido localizadas en India y otros dos más son identificados aquí. Es interesante notar que las posibilidades petroleras en la zona marítima de India coinciden con alguna forma de sistemas triple de placas.