Inorganic forms of mercury (Hg) can be converted by natural processes into methylmercury, a highly potent neurotoxin that can bioaccumulate in food chains and pose a risk to human health. Although Hg can enter aquatic environments through direct deposition, the predominant source derives from complex terrestrial cycling in nearby ecosystem vegetation and soils. Here we assess the spatial distribution of soil and litterfall Hg within two paired catchments of the Shenandoah National Park: the northwest-facing North Fork Dry Run (NFDR) and the southeast-facing Hannah Run (HR) catchments. Litterfall Hg concentrations were not significantly different between the NFDR and HR catchments. This may be attributable to the speciation of Hg (gaseous elemental Hg) that is involved in leaf-level accumulation. Significant differences in soil organic-layer Hg concentrations were observed between the two study catchments, with NFDR soils having roughly 50 % higher Hg concentrations than those from HR. These differences can be explained by differences in soil N content (and to a lesser extent soil C content) between catchments, as both elements exert a strong control of the amount of Hg bound in soils. We found no evidence that topographic aspect contributes to the spatial variability of soil Hg concentrations in these paired catchments, but did detect an influence from elevation. Soils located near ridges in mountainous catchments can contain relatively high Hg concentrations due to (1) lower turnover rates in soil organic matter pools, (2) enhanced deposition, and (3) limited mobilization of Hg from those areas.

Adsorption together with size exclusion and charge attraction/repulsion has to be taken into account when considering removal of pharmaceuticals as emerging contaminants from water by reverse osmosis and nanofiltration membranes. Glucocorticosteroids (hydrocortisone (HYDRO), dexamethasone (DEXA)), anesthetics (procaine, lidocaine) with relatively weak hydrophobicities (1 < log K O/W < 3), and membranes (XLE, LFC–1, CPA3, SWC1, NF90, and NF270) have been investigated in this study. Adsorption was studied by measuring the concentration of compounds in feed and permeate and by monitoring changes in membrane flux in the batch mode operation during 24 h. A decrease in the feed concentrations for HYDRO and DEXA (log K O/W < 2) was observed. The loss of these compounds in feed was associated with irreversible adsorption onto an NF270 and a CPA3 membrane. Therefore, when considering removal of pharmaceuticals with lower hydrophobicity, adsorption has to be particularly taken into account for membranes with bigger pores in the selective layer. Also, a high dipole moment and low water solubility affected adsorption on the membranes. For smaller and slightly more hydrophobic pharmaceuticals (log K O/W > 2), an increase in the feed concentration was obtained. Firstly, these compounds instantly adsorbed to the membrane. Secondly, the compounds diffused through the polymer matrix and desorbed to the permeate side after equilibrium had been reached.

Electrokinetic extraction, which is an emerging technology, can be used for in situ removal of contaminants by the application of a direct current (DC) electric field across the contaminated subsurface soil. In this study, a kaolinite spiked with Pb (720 mg kg-1) was used to investigate the removal of Pb through electrokinetic extraction in the presence or absence of a cation selective membrane (CSM). The contaminated kaolinite was subjected to a constant DC voltage (2 V cm-1) for 4 days. A low DC voltage applied in absence of CSM developed a high pH interface within the electrokinetic cell. The mobility of Pb thus decreased due to the remarkable rise in the pH values. The inclusion of a CSM improved the removal efficiency but could not achieve the critical surface pH (<pH 3.5). The removal efficiency increased in the presence of Ca(NO3)2, such that 95 % of the spiked Pb was extracted from kaolinite, with 88 % of the Pb being recovered from the cathode chambers. In contrast, only 24 % of the spiked Pb was removed in the presence of ethylenediaminetetraacetic acid (EDTA). Moreover, Pb was detected in the anode chamber solution and 60 % of the spiked Pb accumulated at the anode. In the presence of both EDTA and Ca(NO3)2, Pb migrated and accumulated at the anode, thus indicating that Ca has a negligible effect in the presence of EDTA. © 2013 Springer Science+Business Media Dordrecht.

Biowastes and inorganic additives are acknowledged efficient but site-dependent alternatives for in situ metal immobilization. The present study evaluates food waste-based compost, a particularly abundant type of biowaste in South Korea, and zeolite as amendments for increasing pH and reducing metal leaching potential in weathered tailings from an abandoned mine site. Two types of biowaste were used: food waste compost (60 % food waste and 40 % sawdust) and market compost (50 % food waste, 10 % agricultural waste, 10 % manure, and 30 % lime). Materials were thoroughly characterized. Leaching tests were then performed in reactors filled with various mixtures of organic–inorganic amended tailings, over a 4-week period. The in situ metal immobilization efficiency of compost was evaluated based on collected leachate quality. Results indicated that both organic and inorganic materials were successful for increasing pH (from 3.0 to up to 8.1) and metal immobilization, except for Pb and As, with which leaching potential increased in most amended reactors relative to un-amended tailings (up to 43 and 158 %, respectively). Over the duration of the experiment, the cumulative reduction of metal leaching potential ranked as follows: Zn (44–91 %) > Mn (4–76 %) > Cr (20–53 %) > Fe (34–44 %) > Cd (17–43 %) > Al (0.5–24 %). Among mixtures, combined biowaste and zeolite-amended tailings showed the best performance for increasing pH (7.5–8.1) and for metal immobilization. Chemical and biological processes, such as sorption and precipitation processes, were predominant. Overall, the study provides useful data on the efficient use of food waste compost for acid mine drainage prevention in South Korea.

Diesel exhaust particulate matter contains many semivolatile organic compounds (SVOCs) of environmental and health significance. This study investigates the composition, emission rates, and measurement integrity of 25 SVOCs, including polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and diesel biomarkers hopanes and steranes. Diesel engine particulate matter (PM), generated using an engine test bench, three engine conditions, and ultralow sulfur diesel (ULSD), was collected on borosilicate glass fiber filters. Under high engine load, the PM emission rate was 0.102 g/kWh, and emission rates of ΣPAHs (10 compounds), ΣNPAHs (6 compounds), Σhopanes (2 compounds), and Σsteranes (2 compounds) were 2.52, 0.351, 0.02-2 and 1 μg/kWh, respectively. Storage losses were evaluated for three cases: conditioning filters in clean air at 25 C and 33 % relative humidity (RH) for 24 h, storing filter samples (without extraction) wrapped in aluminum foil at 4 C for up to 1 month, and storing filter extracts in glass vials capped with Teflon crimp seals at 4 C for up to 6 months. After conditioning filters for 24 h, 30 % of the more volatile PAHs were lost, but lower volatility NPAHs, hopanes and steranes showed negligible changes. Storing wrapped filters and extracts at 4 C for up to 1 month did not lead to significant losses, but storing extracts for 5 months led to significant losses of PAHs and NPAHs; hopanes and steranes demonstrated greater integrity. These results suggest that even relatively brief filter conditioning periods, needed for gravimetric measurements of PM mass, and extended storage of filter extracts, can lead to underestimates of SVOC concentrations. Thus, SVOC sampling and analysis protocols should utilize stringent criteria and performance checks to identify and limit possible biases occurring during filter and extract processing. © 2013 Springer Science+Business Media Dordrecht.

Chlorine is the most commonly used chemical for water and wastewater disinfection worldwide, and it reacts with both ammonia and dissolved organic nitrogen. Using the salicylate spectrophotometric method, effects of glycine on the classic breakpoint chlorination are studied using glycine as a surrogate for dissolved organic nitrogen. The results show that the shape of the breakpoint chlorination curve with glycine was analogous to that of water without glycine. Increasing the glycine concentration moves the chlorination breakpoint curve to the right, demonstrating that more chlorine must be added to replace the chlorine consumed by glycine and yield the desired residual active chlorine concentration. At the peak of the chlorination breakpoint curve, both NH₂Cl and mono-chlorinated organic chloramine reach their maximum. The Cl₂/N ratio of the peak is linearly related to the glycine concentration, and our calculations indicate that the maximum of mono-chlorinated organic chloramine formation by glycine chlorination occurs at a stoichiometric ratio of 1:1; the same as that for chlorinating ammonia to NH₂Cl. The distribution of NH₂Cl and organic chloramines is controlled by [Gly]/[NH₃-N]. At the breakpoint, ammonia and glycine are completely oxidized by chlorine, which leads to chlorine depletion. The stoichiometric ratio for the complete oxidation of glycine was 3:1, larger than that for complete oxidation of ammonia (2:1). For the different stoichiometric ratio in reaction of oxidation of ammonia and glycine, the sum of ammonia and glycine cannot be used as a chlorine dosage control parameter. The chlorine control method involving ammonia and glycine for chlorine and chloramination process is established.

The present work tested effects of a revegetation pattern conducted using Paulownia fortunei (Seem.) Hemsl. (Scrophulariaceae) on soil chemical properties and actinomycete community structure identified by terminal restriction fragment length polymorphism (T-RFLP) technology of 16S rDNA. The results indicated that P. fortunei planting with time effectively improved organic carbon and total nitrogen contents, as well as pH in heavy metal-contaminated soils and, at the same time, enhanced the retention of heavy metals such as Pb, Zn, Cu and Cd in soils. T-RFLP profiles of soil actinomycete communities digested from two restriction enzymes (HhaI and RsaI) showed different specific TRF patterns across four sites with different revegetation time. Nonetheless, number and diversity of terminal restriction fragments for soil actinomycete community increased gradually with P. fortunei planting time and followed consistent patterns with soil organic carbon, total nitrogen, pH and heavy metal contents. Our results revealed a great potential of P. fortunei to remediate heavy metal-contaminated soils.

One of the major obstacles to zerovalent iron nanoparticles (nZVI) application in soil and groundwater remediation is the limited transport, especially in low-permeability soils. In this study, direct current (constant potential of 5.0 V) was used to enhance polymer-coated nZVI mobility in different porous media, including a bed of glass beads and kaolin clay. The tests were conducted using a modified electrophoretic cell and with nZVI concentrations typical of field applications (4 g L-1). Experimental results indicate that the use of direct current can enhance the transport of the polymer-modified nanoparticles when compared with natural diffusion in low permeability or surface neutral porous medium. The applied electric field appeared to enhance the oxidation-reduction potential, creating a synergistic effect of nZVI usage with electrokinetics. Aggregation of the nanoparticles, observed near the injection point, remained unresolved. © 2013 Springer Science+Business Media Dordrecht.

Copper(II) biosorption in the presence of complexing agents (CA) onto orange peel (OP) and chemically modified OP (OPᴴ⁺, OPᴺᵃ⁺, and OP⁽ᴺᵃ⁺⁾⁽ᴴ⁺⁾) was studied. The study of the effect of pH showed that OPᴴ⁺ presented a copper(II) uptake similar to OP in the pH range 1.5–6.0, whereas OPᴺᵃ⁺ and OP⁽ᴺᵃ⁺⁾⁽ᴴ⁺⁾ showed the highest copper(II) uptake in the pH range 4–6. Copper(II) sorption isotherms were obtained with Cu(II)/CA mass ratios of 1:0 and 1:2 at pH 5. The Sips model fitted best the isotherms without CA, whereas the Freundlich and Brunauer-Emmett-Teller (BET) models fitted best the isotherms in the presence of ethylenediaminetetraacetic acid (EDTA) and citrate, respectively. The CA reduced the copper(II) uptake due to the presence of copper(II)-chelated species, though the interference of citrate was less important than that of EDTA. OPᴺᵃ⁺ and OP⁽ᴺᵃ⁺⁾⁽ᴴ⁺⁾ showed a higher copper(II) uptake capacity than OP, also in the presence of CA in solution. Copper(II) sorption mechanisms were studied using energy-dispersive X-ray and Fourier transform infrared spectroscopy and revealed ion exchange as one of the mechanisms. Biosorption reversibility and biosorbent reuse were evaluated in sorption/desorption cycles. Reversibility of copper(II) sorption was obtained (90 % metal recovery), though an important reduction of the metal uptake was observed in the second cycle.

In this study, chemical oxidation was applied to treat three contaminated sediments. All the sediments were contaminated with mineral oil, polycyclic aromatic hydrocarbons and heavy metals and had an organic matter content ranging from 2.4 to 7.6 %. The natural oxidant demand of the sediments was determined during treatment with two different types of oxidants (potassium permanganate and sodium persulfate), and the effect of these oxidants on the heavy metal release and on the microbial community was investigated. The natural oxidant demands of the sediments under persulfate treatment were lower (30–100 g kg⁻¹) than the ones treated with permanganate (50–450 g kg⁻¹). Cr was released during the application of permanganate whereas Zn and Pb were released under persulfate treatment. qPCR results showed that permanganate and persulfate, both at a concentration of 150 g kg⁻¹, caused a decrease (2 log units) in the number of 16S rRNA gene of total bacteria in the sediment having the lowest organic matter content. However, the total ATP, considered as a biomarker for microbial activity, was below detection limit in all sediments in the presence of at least 150 g kg⁻¹ oxidant. Only permanganate induced a shift in the structure of the microbial community.