Value chain for next-generation biofuels: resilience and sustainability of the product life cycle

Multiple factors including climate change, price uncertainties, and geopolitical instability have prompted many industries to investigate the feasibility of replacing traditional petroleum-based fuels with biofuel alternatives. However, to make this transition successful, these new biofuels must be environmentally sustainable and the necessary support infrastructure must be in place to make the production, distribution, and storage of these biofuels technologically feasible and cost effective. Developing a value chain, spanning from feedstock production to distribution to end users, requires garnering buy-in from multiple stakeholders by demonstrating environmental, economic, and social benefits and incentives. Two critical factors are the environmental benefits achieved from the use of the biofuel technology and the degree of resilience of the value chain to emergent conditions to ensure steady supply to consumers. Moreover, different biofuel pathways have different costs, benefits, and risks which must be compared. In this paper, we describe how environmental sustainability can be modeled using life cycle assessment (LCA) and how the resilience of value chain initiatives can be modeled using a scenario-based decision model. We then describe how sustainability and resilience assessments can be integrated in an iterative, anticipatory LCA framework. These assessments can be used as the basis for a business case for various investments, as well as a means for promoting responsible innovations, with the aviation industry used as a case study.     

Influence of age,season, body condition and geographical area on concentrations of chlorinated and brominated contaminants in wild mink (Neovison vison) in Sweden

The wild mink has gained acceptance as a sentinel species in environmental monitoring. However, only limited data are available in the literature on factors driving variability in concentrations of organic pollutants in this species. This study characterizes the differences in contaminant concentrations in subcutaneous fat of male mink from four different areas in Sweden and demonstrates how age, season and body condition influence concentrations of polychlorinated biphenyl (PCB) congeners, polybrominated diphenyl ether (PBDE) congeners (including methoxylated forms, MeO-PBDEs), as well as the pesticides dichlorodiphenyldichloroethylene (DDE), chlordane and hexachlorobenzene (HCB). The data were statistically treated using multiple regression and principal component analysis. The ∑PCB concentration and concentrations of PCB congeners 138, 156, 157, 180, 170/190, 189, 194, 206, 209 as well as PBDE 153/154 varied with age. Season had an influence on ∑PCB, PBDE 47 and PBDE 153/154 concentrations, as well as concentrations of most PCB congeners, with the exception of PCB 101, 110, 141 and 182/187. Lean mink had higher concentrations of most PCBs and PBDEs than mink with larger fat depots. The analyzed pesticides (DDE, oxychlordane, HCB) showed no systematic variation with season, age or body condition. The concentrations of MeO-PBDEs were generally low and 6MeO-PBDE 47 was the most commonly detected MeO-PBDE in mink from marine, brackish and freshwater areas. The results indicate that age, season and body condition are factors that may influence the concentrations of PCBs and PBDEs, and it is thus recommended to take these factors into account when analyzing mink exposure data.     

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na⁺ and Ca²⁺ on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH = 7. Isotherms for the beta-blocker metoprolol were obtained by sediment–water batch tests over a wide concentration range (1–100 000 μg L^?1). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n = 0.9), indicating slightly non-linear behavior. Results show that the influence of Ca²⁺ compared to Na⁺ is more pronounced. A logarithmic correlation between the Freundlich coefficient K_Fr and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.     

Earthworm ecotoxicological assessments of pesticides used to treat seeds under tropical conditions

Ecotoxicological laboratory tests (lower-tier tests) are fundamental tools for assessing the toxicity of pesticides to soil organisms. In this study, using these tests under tropical conditions, we quantified the impact of the insecticides imidacloprid, fipronil, and thiametoxam, and the fungicides captan and carboxin + thiram, all of which are used in the chemical treatment of crop seeds, on the survival, reproduction, and behavior of Eisenia andrei (Oligochaeta). With the exception of imidacloprid, none of the pesticides tested caused mortality in E. andrei in artificial soils. The LC₅₀ of imidacloprid was estimated as 25.53 mg active ingredient kg^?1 of dry soil. Earthworm reproduction rates were reduced by imidacloprid (EC₅₀ = 4.07 mg kg^?1), fipronil (EC₂₀ = 23.16 mg kg^?1), carboxin + thiram (EC₅₀ = 56.38 mg kg^?1), captan (EC₅₀ = 334.84 mg kg^?1), and thiametoxam (EC₅₀ = 791.99 mg kg^?1). Avoidance behavior was observed in the presence of imidacloprid (AC₅₀ = 0.11 mg kg^?1), captan (AC₅₀ = 33.54 mg kg^?1), carboxin + thiram (AC₅₀ = 60.32 mg kg^?1), and thiametoxam (AC₅₀ = >20 mg kg^?1). Earthworms showed a preference for soils with the insecticide fipronil. Imidacloprid was the most toxic of the substances tested for E. andrei. The avoidance test was the most sensitive test for most pesticides studied, but results varied between pesticides. These results offer new insights on the toxicity of pesticides used to treat seeds in tropical regions. However, they should be complemented with higher-tier tests in order to reduce the uncertainties in risk assessment.     

Impact of long‐term pesticide applications on some soil biological parameters

Abstract

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (São Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)‐activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron‐oxide reduction, and the microbial biomass was estimated by the substrate (glucose)‐indiced respiration. Increases in DHA‐activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron‐reduction. In the experimental field soil, the increases in DHA‐activity were followed only by decreases in iron‐reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

A preliminary examination of the translocation of microencapsulated cyfluthrin following applications to the perimeter of residential dwellings

Abstract

Methods have been developed to monitor the translocation of microencapsulated cyfluthrin following perimeter applications to residential dwellings. A pilot study was implemented to determine both the potential for application spray to drift away from dwellings and the intrusion of residues into homes following perimeter treatments. Residential monitoring included measuring spray drift using cellulose filter paper and the collection of soil samples from within the spray zone. In addition, interior air was monitored using fiberglass filter paper as a sorbent medium and cotton ball swabs were used to collect surface wipes.

Fortification of matrixes resulted in recoveries of >90%. Spray drift was highest at the point of application and declined to low but measurable levels 9.1m from the foundations of dwellings. Soil residues declined to low, but measurable levels by 45 days post‐application. No cyfluthrin was measured from indoor air; however, some interior surfaces had detectable levels of cyfluthrin until three days post‐application.

Findings indicate that spray drift resulting from perimeter applications might contaminate non‐target surfaces outside the spray zone. Soil borne residues may serve as persistent sources for human exposure and potentially intrude into dwellings through the activities of occupants and pets. Residues do not appreciably translocate through air and consequently inhalation is not a likely route for human exposure. Surface residues detected indoors suggest that the physical movement of residues from the exterior to the interior might be a viable route of movement of residues following this type of application.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure,biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, ¹³C and 1H Nuclear Magnetic Resonance Spectrometry (¹³C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) ¹³C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Impact of redox conditions on metolachlor and metribuzin degradation in mississippi flood plain soils

Abstract

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd^‐1 and 25 ngd^‐1, respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd^‐1 and 32.5 ngd^‐1, respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd^‐1 and 12.0 ngd^‐1 for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd^‐1 and 5.35 ngd^‐1. Metribuzin degraded faster (12.0 ngd^‐1) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd^‐1).