Effects of different organic substrate compositions on the decontamination of aged PAH-polluted soils through outdoor co-composting.

The effects of different organic substrate compositions on the efficiency of outdoor co-composting as a bioremediation technology for decontaminating soil polluted by polycyclic aromatic hydrocarbons (PAHs) were investigated. Four different substrate mixtures and two different aged PAH-contaminated soils were used in a semi-pilot-scale experiment that lasted nearly 700 days. The two soils (A and B) differed concerning both the initial concentrations of the Æ©16 US EPA PAHs (5926 vs. 369 mg kg-1, respectively) and the type of predominant PAH group by molecular weight. The experiments revealed that while the composition of the organic substrate had an impact on the rate of PAH degradation, it did not significantly influence the final extent of PAH degradation. Notably, the organic substrate consisting of green waste and wood chips (GW) was found to facilitate the most rapid rate of PAH degradation (first-order rate constant k = 0.033 ± 0.000 d-1 with soil A over the initial 42 days of the experiment and k = 0.036 ± 0.000 d-1 with soil B over the initial 56 days). Despite the differences in organic substrate compositions and types of soil being treated, PAH degradation levels exceeded at least 95% in all the treatments after more than 680 days of co-composting. Regardless of the composition, the removal of low- and medium- molecular-weight (2-4 rings) PAHs was nearly complete by the end of the experiment. Furthermore, high-molecular-weight PAHs (5 rings and more) were significantly degraded during co-composting, with reductions ranging from 54% to 79% in soil A and from 59% to 68% in soil B. All composts were dominated by Proteobacteria, Firmicutes, and Actinobacteria, with significant differences in abundance between soils. Genera with PAH degradation potentials were detected in all samples. The results of a battery of toxicity tests showed that there was almost no toxicity associated with the final composts.

Remedial trial of sequential anoxic/oxic chemico-biological treatment for decontamination of extreme hexachlorocyclohexane concentrations in polluted soil.

During production of γ-hexachlorocyclohexane (γ-HCH), thousands of tons of other isomers were synthesized as byproducts, and after dumping represent sources of contamination for the environment. Several microbes have the potential for aerobic and anaerobic degradation of HCHs, and zero-valent iron is an effective remediation agent for abiotic dechlorination of HCHs, whereas the combination of the processes has not yet been explored. In this study, a sequence of anoxic/oxic chemico-biological treatments for the degradation of HCHs in a real extremely contaminated soil (10-30 g/kg) was applied. Approximately 1500 kg of the soil was employed, and various combinations of reducing and oxygen-releasing chemicals were used for setting up the aerobic and anaerobic phases. The best results were obtained with mZVI/nZVI, grass cuttings, and oxygen-releasing compounds. In this case, 80 % removal of HCHs was achieved in 129 days, and 98 % degradation was achieved after 1106 days. The analysis of HCHs and their transformation products proved active degradation when slight accumulation of the transformation product during the anaerobic phase was followed by aerobic degradation. The results document that switching between aerobic and anaerobic phases, together with the addition of grass, also created suitable conditions for the biodegradation of HCHs and monochlorobenzene/benzene by microbes.

The effects of hydraulic/pneumatic fracturing-enhanced remediation (FRAC-IN) at a site contaminated by chlorinated ethenes: A case study.

A low-permeability locality with heterogeneous geology contaminated primarily by tetrachloroethene (PCE) present partially in the free phase in the unsaturated zone was treated on a pilot scale via direct push pneumatic fracturing combined with the hydraulic delivery of a remediation suspension consisting of milled iron, sulphidated nanosized zerovalent iron and sand in guar gum solution. Afterwards, a whey solution was injected into the fractures as a carbon source for bacteria. The unsaturated and saturated zones were treated. Long-term monitoring of the groundwater revealed that the abiotic reduction of PCE and trichloroethene was the dominant remediation processes for several months after the injections. A complex microbial consortium was developed that was capable of effective, long-term chlorinated ethenes (ClE) dechlorination. The consortium consisted mainly of Dehalococcoides but also of other anaerobic bacterial strains capable of partial dechlorination of ClE, including the sulphate-reducing bacteria; Geobacter and Desulfitobacterium. The average chlorine number in the groundwater decreased from 3.65 to 1.38 within 2.5 years after the injections, while the average ClE concentration increased from 13.5 to 31.5 mgL-1 because of the substantial acceleration of the ClE mass-transfer to the groundwater caused by the treatment. The remediation processes remained fully active for 2.5 years.

Assessment of biodegradation potential at a site contaminated by a mixture of BTEX, chlorinated pollutants and pharmaceuticals using passive sampling methods - Case study.

The present study describes a pilot remediation test of a co-mingled plume containing BTEX, chlorinated pollutants and pharmaceuticals. Remediation was attempted using a combination of various approaches, including a pump and treat system applying an advanced oxidation process and targeted direct push injections of calcium peroxide. The remediation process was monitored intensively and extensively throughout the pilot test using various conventional and passive sampling methods, including next-generation amplicon sequencing. The results showed that the injection of oxygen-saturated treated water with residual hydrogen peroxide and elevated temperature enhanced the in situ removal of monoaromatics and chlorinated pollutants. In particular, in combination with the injection of calcium peroxide, the conditions facilitated the in situ bacterial biodegradation of the pollutants. The mean groundwater concentration of benzene decreased from 1349µg·L-1 prior to the test to 3µg·L-1 within 3months after the calcium peroxide injections; additionally, monochlorobenzene decreased from 1545µg·L-1 to 36µg·L-1, and toluene decreased from 143µg·L-1 to 2µg·L-1. Furthermore, significant degradation of the contaminants bound to the soil matrix in less permeable zones was observed. Based on a developed 3D model, 90% of toluene and 88% of chlorobenzene bound to the soil were removed during the pilot test, and benzene was removed almost completely. On the other hand, the psychopharmaceuticals were effectively removed by the employed advanced oxidation process only from the treated water, and their concentration in groundwater remained stagnant due to inflow from the surroundings and their absence of in situ degradation. The employment of passive sampling techniques, including passive diffusion bags (PDB) for volatile organic pollutants and their respective transformation products, polar organic compound integrative samplers (POCIS) for the pharmaceuticals and in situ soil microcosms for microbial community analysis, was proven to be suitable for monitoring remediation in saturated zones.

Pharmaceuticals, benzene, toluene and chlorobenzene removal from contaminated groundwater by combined UV/H2O2 photo-oxidation and aeration.

This study was performed to test the feasibility of several decontamination methods for remediating heavily contaminated groundwater in a real contaminated locality in the Czech Republic, where a pharmaceuticals plant has been in operation for more than 80 years. The site is polluted mainly by recalcitrant psychopharmaceuticals and monoaromatic hydrocarbons, such as benzene, toluene and chlorobenzene. For this purpose, an advanced oxidation technique employing UV radiation with hydrogen peroxide dosing was employed, in combination with simple aeration pretreatment. The results showed that UV/H2O2 was an efficient and necessary step for degradation of the pharmaceuticals; however, the monoaromatics were already removed during the aeration step. Characterization of the removal mechanisms participating in the aeration revealed that volatilization, co-precipitation and biodegradation contributed to the process. These findings were supported by bacterial metabolite analyses, phospholipid fatty acid analysis, qPCR of representatives of the degradative genes and detailed characterization of the formed precipitate using Mössbauer spectroscopy and scanning electron microscopy. Further tests were carried out in a continuous arrangement directly connected to the wells already present in the locality. The results documented the feasibility of combination of the photo-reactor employing UV/H2O2 together with aeration pretreatment for 4 months, where the overall decontamination efficiency ranged from 72% to 99% of the pharmaceuticals. We recorded even better results for the monoaromatics decontamination except for one month, when we encountered some technical problems with the aeration pump. This demonstrated the necessity of using the aeration step.

Method for analysis of psychopharmaceuticals in real industrial wastewater and groundwater with suspended organic particulate matter using solid phase extraction disks extraction and ultra-high performance liquid chromatography/time-of-flight mass spectrometry.

A rapid and reliable analytical method was developed for the quantitative determination of psychopharmaceuticals, their precursors and by-products in real contaminated samples from a pharmaceutical company in Olomouc (Czech Republic), based on SPE disk extraction and detection by ultra performance liquid chromatography, combined with time-of-flight mass spectrometry. The target compounds were quantified in the real whole-water samples (water including suspended particles), both in the presence of suspended particulate matter (SPM) and high concentrations of other organic pollutants. A total of nine compounds were analyzed which consisted of three commonly used antidepressants (tricyclic antidepressants and antipsychotics), one antitussive agent and five by-products or precursors. At first, the SPE disk method was developed for the extraction of water samples (dissolved analytes, recovery 84-104%) and pressurised liquid extraction technique was verified for solid matrices (sludge samples, recovery 81-95%). In order to evaluate the SPE disk technique for whole water samples containing SPM, non contaminated groundwater samples were also loaded with different amounts (100 and 300mgL(-1)) of real contaminated sludge originating from the same locality. The recoveries from the whole-water samples obtained by SPE disk method ranged between 67 and 119% after the addition of the most contaminated sludge. The final method was applied to several real groundwater (whole-water) samples from the industrial area and high concentrations (up to 10(3)µgL(-1)) of the target compounds were detected. The results of this study document and indicate the feasibility of the SPE disk method for analysis of groundwater.

Combined nano-biotechnology for in-situ remediation of mixed contamination of groundwater by hexavalent chromium and chlorinated solvents.

The present report describes a 13month pilot remediation study that consists of a combination of Cr(VI) (4.4 to 57mg/l) geofixation and dechlorination of chlorinated ethenes (400 to 6526µg/l), achieved by the sequential use of nanoscale zerovalent iron (nZVI) particles and in situ biotic reduction supported by whey injection. The remediation process was monitored using numerous techniques, including physical-chemical analyses and molecular biology approaches which enabled both the characterization of the mechanisms involved in pollutant transformation and the description of the overall background processes of the treatment. The results revealed that nZVI was efficient toward Cr(VI) by itself and completely removed it from the groundwater (LOQ 0.05mg/l) and the subsequent application of whey resulted in a high removal of chlorinated ethenes (97 to 99%). The persistence of the reducing conditions, even after the depletion of the organic substrates, indicated a complementarity between nZVI and the whey phases in the combined technology as the subsequent application of whey phase partially assisted the microbial regeneration of the spent nZVI by promoting its reduction into Fe(II), which further supported remediation conditions at the site. Illumina sequencing and the detection of functional vcrA and bvcA genes documented a development in the reducing microbes (iron-reducing, sulfate-reducing and chlororespiring bacteria) that benefited under the conditions of the site and that was probably responsible for the high dechlorination and/or Cr(VI) reduction. The results of this study demonstrate the feasibility and high efficiency of the combined nano-biotechnological approach of nZVI and whey application in-situ for the removal of Cr(VI) and chlorinated ethenes from the groundwater of the contaminated site.

Combined abiotic and biotic in-situ reduction of hexavalent chromium in groundwater using nZVI and whey: A remedial pilot test.

The paper describes a pilot remediation test combining two Cr(VI) geofixation methods - chemical reduction by nanoscale zero-valent iron (nZVI) and subsequent biotic reduction supported by whey. Combination of the methods exploited the advantages of both - a rapid decrease in Cr(VI) concentrations by nZVI, which prevented further spreading of the contamination and facilitated subsequent use of the cheaper biological method. Successive application of whey as an organic substrate to promote biotic reduction of Cr(VI) after application of nZVI resulted in a further and long-term decrease in the Cr(VI) contents in the groundwater. The effect of biotic reduction was observed even in a monitoring well located at a distance of 22 m from the substrate injection wells after 10 months. The results indicated a reciprocal effect of both the phases - nZVI oxidized to Fe(III) during the abiotic phase was microbially reduced back to Fe(II) and acted as a reducing agent for Cr(VI) even when the microbial density was already low due to the consumed substrate. Community analysis with pyrosequencing of the 16S rRNA genes further confirmed partial recycling of nZVI in the form of Fe(II), where the results showed that the Cr(VI) reducing process was mediated mainly by iron-reducing and sulfate-reducing bacteria.

Nanoscale zero-valent iron application for in situ reduction of hexavalent chromium and its effects on indigenous microorganism populations.

Because of its high toxicity and mobility, hexavalent chromium is considered to be a high priority pollutant. This study was performed to carry out a pilot-scale in-situ remediation test in the saturated zone of a historically Cr(VI)-contaminated site using commercially available nanoscale zero-valent iron (nZVI). The site was monitored before and after the nZVI application by means of microbial cultivation tests, phospholipid fatty acid analysis (PLFA) and toxicological tests with Vibrio fischeri. Injection of nZVI resulted in a rapid decrease in the Cr(VI) and total Cr concentrations in the groundwater without any substantial effect on its chemical properties. The ecotoxicological test with V. fischeri did not indicate any negative changes in the toxicity of the groundwater following the application of nZVI and no significant changes were observed in cultivable psychrophilic bacteria densities and PLFA concentrations in the groundwater samples during the course of the remediation test. However, PLFA of soil samples revealed that the application of nZVI significantly stimulated the growth of Gram-positive bacteria. Principle component analysis (PCA) was applied to the PLFA results for the soil samples from the site in order to explain how Cr(VI) reduction and the presence of Fe influence the indigenous populations. The PCA results clearly indicated a negative correlation between the Cr concentrations and the biota before the application of nZVI and a significant positive correlation between bacteria and the concentration of Fe after the application of nZVI.