Lignin-Based Pesticide Delivery System.

The potential of lignosulfonates as widely underutilized byproducts of the pulp and paper industry for the synthesis of a biodegradable pesticide carrier system was assessed in this study. Design of experiment software MODDE Pro was for the first time applied to optimize lignosulfonate granule production using Myceliophthora thermophila laccase as a biocatalyst. Enzymatic cross-linking was monitored using size exclusion chromatography coupled online to multiangle laser light scattering, viscosity measurement, and enzyme activity. The determined optimal and experimentally confirmed incubation conditions were: 33 °C, 30 cm3/min O2 supply, and 190 min reaction time. The granules were thereafter loaded with 2 g/kg 3,6-dichloro-2-methoxybenzoic acid (Dicamba), a broad-spectrum herbicide. According to the HPLC analysis, complete release of Dicamba was achieved after 48 h of release. This study showed the green production of a 100% lignosulfonate-based biodegradable solid carrier with potential application in agriculture.

Enhanced Accessibility of Polycyclic Aromatic Hydrocarbons (PAHs) and Heterocyclic PAHs in Industrially Contaminated Soil after Passive Dosing of a Competitive Sorbate.

To assess the exposure to polycyclic aromatic hydrocarbons (PAHs) it is important to understand the binding mechanisms between specific soil constituents and the organic pollutant. In this study, sorptive bioaccessibility extraction (SBE) was applied to quantify the accessible PAH fraction in industrially contaminated soil with and without passive dosing of a competitive sorbate. SBE experiments revealed an accessible PAH fraction of 41 ± 1% (∑16 US EPA PAHs + 5 further PAHs). The passive dosing of toluene below its saturation level revealed competitive binding and resulted in an average increase of the accessible fraction to 49 ± 2%, whereby primarily the accessibility of higher molecular weight PAHs (log Kow > 6) was affected. Competitive binding was verified using the same soil with only desorption-resistant PAHs present. In this experiment, passive dosing of toluene resulted in desorption of 13 ± 0.4% PAH. We explain increased PAH desorption after addition of toluene by competitive adsorption to high-affinity sorption sites while acknowledging that toluene could additionally have increased PAH mobility within the soil matrix. Findings suggest that the presence of copollutants at contaminated sites deserves specific considerations as these may increase accessibility and thereby exposure and mobility of PAHs.

Changes in iso- and n-alkane distribution during biodegradation of crude oil under nitrate and sulphate reducing conditions.

Crude oil consists of a large number of hydrocarbons with different susceptibility to microbial degradation. The influence of hydrocarbon structure and molecular weight on hydrocarbon biodegradation under anaerobic conditions is not fully explored. In this study oxygen, nitrate and sulphate served as terminal electron acceptors (TEAs) for the microbial degradation of a paraffin-rich crude oil in a freshly contaminated soil. During 185 days of incubation, alkanes from n-C11 to n-C39, three n- to iso-alkane ratios commonly used as weathering indicators and the unresolved complex mixture (UCM) were quantified and statistically analyzed. The use of different TEAs for hydrocarbon degradation resulted in dissimilar degradative patterns for n- and iso-alkanes. While n-alkane biodegradation followed well-established patterns under aerobic conditions, lower molecular weight alkanes were found to be more recalcitrant than mid- to high-molecular weight alkanes under nitrate-reducing conditions. Biodegradation with sulphate as the TEA was most pronounced for long-chain (n-C32 to n-C39) alkanes. The observation of increasing ratios of n-C17 to pristane and of n-C18 to phytane provides first evidence of the preferential degradation of branched over normal alkanes under sulphate reducing conditions. The formation of distinctly different n- and iso-alkane biodegradation fingerprints under different electron accepting conditions may be used to assess the occurrence of specific degradation processes at a contaminated site. The use of n- to iso-alkane ratios for this purpose may require adjustment if applied for anaerobic sites.

Comprehensive GC²/MS for the monitoring of aromatic tar oil constituents during biodegradation in a historically contaminated soil.

The constituents of tar oil comprise a wide range of physico-chemically heterogeneous pollutants of environmental concern. Besides the sixteen polycyclic aromatic hydrocarbons defined as priority pollutants by the US-EPA (EPA-PAHs), a wide range of substituted (NSO-PAC) and alkylated (alkyl-PAC) aromatic tar oil compounds are gaining increased attention for their toxic, carcinogenic, mutagenic and/or teratogenic properties. Investigations on tar oil biodegradation in soil are in part hampered by the absence of an efficient analytical tool for the simultaneous analysis of this wide range of compounds with dissimilar analytical properties. Therefore, the present study sets out to explore the applicability of comprehensive two-dimensional gas chromatography (GC²/MS) for the simultaneous measurement of compounds with differing polarity or that are co-eluting in one-dimensional systems. Aerobic tar oil biodegradation in a historically contaminated soil was analyzed over 56 days in lab-scale bioslurry tests. Forty-three aromatic compounds were identified with GC²/MS in one single analysis. The number of alkyl chains on a molecule was found to prime over alkyl chain length in hampering compound biodegradation. In most cases, substitution of carbon with nitrogen and oxygen was related to increased compound degradation in comparison to unalkylated and sulphur- or unsubstituted PAH with a similar ring number.The obtained results indicate that GC²/MS can be employed for the rapid assessment of a large variety of structurally heterogeneous environmental contaminants. Its application can contribute to facilitate site assessment, development and control of microbial cleanup technologies for tar oil contaminated sites.

A contaminant trap as a tool for isolating and measuring the desorption resistant fraction of soil pollutants.

Bioremediation of contaminated soils often leaves a desorption-resistant pollutant fraction behind in the soil, which in the present study was isolated with a combination of diffusive carrier and infinite diffusive sink. Such a diffusive sink was made by casting a composite of silicone and activated carbon into the bottom of a large glass. Field-contaminated soil samples were then suspended in a cyclodextrin solution and incubated in such glasses for the continuous trapping of PAH molecules during their release from the soil matrix. The PAH concentrations remaining in the soil were determined by exhaustive extraction and compared with a biodegradation experiment. The concentration decline in the first soil was faster in the contaminant trap than in the biodegradation experiment, but the halting of the biodegradation process before reaching the legal threshold level was well indicated by the contaminant trap. The PAH concentrations in the second soil hardly decreased in the traps at all, in good agreement with the biodegradation experiment. The PAHs in this soil appeared to be "stuck" by strong sorption. The contaminant trap proved to be a practical approach to the isolation and quantification of the desorption-resistant PAH fraction.

Potential of preliminary test methods to predict biodegradation performance of petroleum hydrocarbons in soil.

Preliminary tests at different scales such as degradation experiments (laboratory) in shaking flasks, soil columns and lysimeters as well as in situ respiration tests (field) were performed with soil from two hydrocarbon contaminated sites. Tests have been evaluated in terms of their potential to provide information on feasibility, degradation rates and residual concentration of bioremediation in the vadose zone. Sample size, costs and duration increased with experimental scale in the order shaking flasks - soil columns - lysimeter - in situ respiration tests, only time demand of respiration tests was relatively low. First-order rate constants observed in degradation experiments exhibited significant differences between both, different experimental sizes and different soils. Rates were in line with type and history of contamination at the sites, but somewhat overestimated field rates particularly in small scale experiments. All laboratory experiments allowed an estimation of residual concentrations after remediation. In situ respiration tests were found to be an appropriate pre-testing and monitoring tool for bioventing although residual concentrations cannot be predicted from in situ respiration tests. Moreover, this method does not account for potential limitations that might hamper biodegradation in the longer term but only reflects the actual degradation potential when the test is performed.

Sequential supercritical fluid extraction (SSFE) for estimating the availability of high molecular weight polycyclic aromatic hydrocarbons in historically polluted soils.

Sequential supercritical fluid (CO2) extraction (SSFE) was applied to eight historically contaminated soils from diverse sources with the aim to elucidate the sorption-desorption behavior of high molecular weight polycyclic aromatic hydrocarbons (PAHs). The method involved five extraction phases applying successively harsher conditions by increasing fluid temperature and density mobilizing target compounds from different soil particle sites. Two groups of soils were identified based on readily desorbing (available) PAH fractions obtained under mildest extraction conditions (e.g., readily desorbing fractions of fluoranthene and pyrene significantly varied between the soils ranging from <10 to >90%). Moreover, extraction behavior strongly correlated with molecular weight revealing decreasing available PAH fractions with increasing weight. Physicochemical soil parameters such as particle size distribution and organic dry mass were found to have no distinct effect on the sorption-desorption behavior of PAHs in the different soils. However, PAH profiles significantly correlated with readily available pollutant fractions; soils with relatively less mobile PAHs had higher proportions of five- and six-ring PAHs and vice versa. Eventually, biodegradability corresponded well with PAH recoveries under the two mildest extraction phases. However, a quantitative relationship was only established for soils with biodegradable PAHs. Out of eight soils, five showed no biodegradation including the four soils with the lowest fraction of readily desorbing PAHs. Only one soil (which was found to be highly toxic to Vibrio fischeri) did not match the overall pattern showing no PAH biodegradability but large fractions of highly mobile PAHs, concluding that mass transfer limitations may only be one of many factors governing biodegradability of PAHs.

Behavior of PAHs during cold storage of historically contaminated soil samples.

The stability of historically polycyclic aromatic hydrocarbon (PAH)-contaminated soils during cold storage was investigated. Samples from two former manufactured gas plants exhibited quantitative recoveries of PAHs over the whole period of sample holding at 4 degrees C in the dark (8-10 months), whereas significant losses of PAHs were observed for soils received from a former railroad sleeper preservation plant with low molecular weight compounds being notably more affected compared to heavier PAHs. Already after 2 weeks of holding time, 3-ring PAHs in one of theses samples were down to 29-73% of the initial concentration and significant losses were observed for up to 5-ring compounds. Dissipation of PAHs was found to be predominantly due to aerobic microbial metabolism since sodium azide poisoned samples showed quantitative recoveries for all PAHs over the entire storage time of 3 months. A similar stabilizing effect was observed for freezing at -20 degrees C as means of preservation. Except for acenaphthene, no significant loss for any of the PAHs was observed over 6 weeks of holding time. Eventually, selected chemical, physical, and biological parameters of two soils were investigated and identified as potential indicators for the stability of PAH-contaminated soil samples.