Alternative end-of-life options for disposable bioplastic products: Degradation and ecotoxicity assessment in compost and soil.

Four different end-of-life options for disposable bioplastic cups were investigated and compared based on their environmental implications. Two products with distinct polymeric composition were tested simulating the following scenarios at laboratory scale: i) industrial composting (180 days at 58 °C); ii) anaerobic digestion followed by industrial composting (45 days at 55 °C and 180 days at 58 °C); iii) anaerobic digestion followed by direct digestate use on soil for agricultural purposes (45 days at 55 °C and 180 days at 25 °C); iv) uncontrolled release into a soil environment (180 days at 25 °C). Ecotoxicity tests were run at the end of each experiment to investigate the effects of the materials on three main groups of terrestrial model organisms: plants, earthworms and nitrifying bacteria. Complete biodegradation of the cups was observed in 180 days in the scenarios involving composting environment. A low degree of biodegradation (22.9 ± 4.5%) of the digestates in soil was observed, warning for a potential micro-bioplastics discharge into the environment. No degradation was observed for the cups in soil during the same testing period. Ecotoxicity tests revealed a negative effect on plants biomass growth across all samples, which was 17-30% lower compared to the blank sample. The experimental campaign highlighted the need for a systematic assessment of controlled treatment of bioplastics, as well as the need for a harmonized legislative framework.

Factor-based assessment of continuous bio-H2 production from cheese whey.

Despite having been widely investigated, dark fermentative H2 production from organic residues is still limited by process-related issues which may hamper the perspectives of full-scale process implementation. Such constraints are mainly due to the process complexity, which is largely affected by multiple and often mutually interacting factors. In the present work, the results of continuous fermentative H2 production experiments using synthetic cheese whey as the input substrate were used to gain detailed knowledge of the process features and identify suitable and critical operating conditions. Specifically, innovative process interpretation involved a combination of analytical characterization of the fermentation broth, mass balance calculations and statistical methods (correlation and principal component analyses) to derive systematic considerations for process characterization and scale-up. The metabolic products mainly included acetate and butyrate, which however were likely to derive (in different proportions depending on the operating conditions) from both hydrogenogenic and competing pathways. For some tests, lactate and succinate were also found to have been formed. It was observed that the main features of the process (H2 yield and rate, stability condition) were correlated with the operational and analytical parameters. The first three principal components identified by the statistical analysis were able to account for: 1) the effect of retention time and total metabolites produced; 2) biogas (H2 and CO2) generation, butyrate production and stability condition; and 3) organic loading rate and propionate production. The results suggested that the main features of hydrogenogenic fermentation can be described by a reduced set of factors that may be usefully adopted for both process monitoring and prediction purposes.

Chemical activation in view of MSWI bottom ash recycling in cement-based systems.

In the present study, the feasibility of recycling incinerator bottom ash in cementitious systems by means of chemical activation was investigated. Different Na-, K- and Ca-based hydroxides and salts were selected for the experiments on the basis of their recognized effects on activation of typical pozzolanic materials. The evolution of mechanical properties of bottom ash/Portland cement mixtures and the leaching of trace metals from the materials were a matter of major concern. The experiments were arranged according to a full factorial design, which also allowed to derive a predictive model for unconfined compressive strength as affected by bottom ash content as well as activator type and dosage. Among the activators tested, calcium chloride was found to affect mechanical strength far more positively than the other species used, at the same time ensuring low metal release from the material. On the other hand, the use of potassium sulfate was observed to cause a significant increase in metal leaching at pH<12, which was probably associated to the release of contaminants initially immobilized within the structure of ettringite as soon as it converted into monosulfate over time.

Fermentative H2 production from food waste: Parametric analysis of factor effects.

Factorial fermentation experiments on food waste (FW) inoculated with activated sludge (AS) were conducted to investigate the effects of pH and the inoculum-to-substrate ratio (ISR [g VSAS/g TOCFW]) on biohydrogen production. The two parameters affected the H2 yield, the fermentation rate and the biochemical pathways. The minimum and maximum yields were 41 L H2/kg TOCFW (pH = 7.5, ISR = 1.74) and 156-160 L H2/kg TOCFW (pH = 5.5, ISR = 0.58 and 1.74). The range of carbohydrates conversion into H2 was 0.37-1.45 mol H2/mol hexose, corresponding to 9.4-36.2% of the theoretical threshold. A second-order predictive model for H2 production identified an optimum region at low pHs and high ISRs, with a theoretical maximum of 168 L H2/kg TOCFW at pH = 5.5 and ISR = 1.74. The Spearman's correlation method revealed several relationships between the variables, suggesting the potentially governing metabolic pathways, which turned out to involve both hydrogenogenic pathways and competing reactions.

Control of fermentation duration and pH to orient biochemicals and biofuels production from cheese whey.

Batch dark fermentation tests were performed on sheep cheese whey without inoculum addition at different operating pHs, relating the type and production yields of the observed gaseous and liquid by-products to the evolution of fermentation. Cheese whey fermentation evolved over time in two steps, involving an initial conversion of carbohydrates to lactic acid, followed by the degradation of this to soluble and gaseous products including short-chain fatty acids (mainly acetic, butyric and propionic acids) and hydrogen. The operating pH affected the production kinetics and yields, as well as the fermentation pathways. By varying the duration of the fermentation process, different cheese whey exploitation strategies may be applied and oriented to the main production of lactic acid, hydrogen or other organic acids.

Combined application of Life Cycle Assessment and linear programming to evaluate food waste-to-food strategies: Seeking for answers in the nexus approach.

The great concern regarding food loss (FL) has been studied previously, but in an isolated way, disregarding interdependencies with other areas. This paper aims to go a step further by proposing a new procedure to assess different waste management alternatives based on the nexus approach by means of an integrated Water-Energy-Food-Climate Nexus Index (WEFCNI). The environmental profile of the waste management techniques is determined using Life Cycle Assessment (LCA) which, in combination with Linear Programming (LP), explores the optimal aggregation of weighting factors that lead to an aggregated nexus index. The management of residues from the anchovy canning industry in Cantabria (Spain) has been used as a case study, considering the three current applied alternatives: (i) valorisation of FL as animal feed in aquaculture (food waste-to-food approach), (ii) incineration of FL with energy recovery, and (iii) landfilling with biogas recovery. The last two considered the use of energy recovered to produce a new aquaculture product (food waste-to-energy-to-food scenarios). The results indicate that incineration is the best performing scenario when the nutritional energy provided by the valorisation alternative is not high enough and the valorisation technology presents the highest water consumption. Therefore, a minimisation in the consumption of natural resources is suggested in order to improve the application of circular economy within the sector. The use of the nexus index as an environmental management tool is extendable to any food system with the aim of facilitating the decision-making process in the development of more sustainable products.

The effect of operating variables on chelant-assisted remediation of contaminated dredged sediment.

The paper shows the results from a number of lab-scale washing treatments using the four chelating agents EDTA, NTA, citric acid and [S,S]-EDDS aiming at the remediation of a real heavy metal-contaminated sediment. Investigation of the influence of chelant type and concentration as well as solution pH was the major focus of the work. The analysis of speciation of metals and chelating agents in solution was carried out through geochemical speciation modelling in order to identify the optimal conditions for the washing process as well as to evaluate the competition phenomena of metal-chelant complexes in solution. The major competing cations were found to be Ca above all and Mg under specific conditions. Among the investigated chelating agents, EDDS appeared to be less affected by competition by major cations while ensuring adequate heavy metal extraction efficiencies. For a 1:1 chelant/metal ratio, the following ranking was observed: EDDS>Cit>NTA>EDTA for As, EDDS>NTA congruent withEDTA>>Cit for Cu, EDDS congruent withEDTA congruent withNTA>Cit for Zn, EDTA>NTA>EDDS>Cit for Pb at pH 5 and EDTA congruent withEDDS congruent withNTA>>Cit for Pb at pH 8. For a 10:1 chelant/metal ratio geochemical modelling indicated that at the equilibrium the extracting solutions were dominated by the free form of the chelating agents, indicating the inability of such species to complex trace metals due the strong interactions existing between heavy metal ions and sediment constituents.

A kinetic study of chelant-assisted remediation of contaminated dredged sediment.

A study on the remediation of a real heavy metal-contaminated sediment was conducted using the four chelating agents ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), citric acid and the S,S-isomer of the ethylenediaminedisuccinic acid ([S,S]-EDDS). Different chelant washing experiments were carried out at a chelant/total metal content of 1 and 10 mol/mol for treatment durations from 0.5 to 48 h to study the extraction kinetics of trace metals and major cations. The objective was to evaluate the removal efficiency of conventional chelating agents as compared to innovative, biodegradable species. Among the target contaminants, Cd, Cu, Pb and Zn were found to be adequately removed by both EDTA and EDDS, while NTA and citric acid yielded unsatisfactory results in some cases. It was also found that As was a critical contaminant which would require an additional specific treatment step, since the residual concentrations after the washing treatment were still far above the regulatory limit values.

Leaching modelling of slurry-phase carbonated steel slag.

In the present work the influence of accelerated mineral carbonation on the leaching behaviour of basic oxygen furnace steel slag was investigated. The environmental behaviour of the material as evaluated through the release of major elements and toxic metals under varying pH conditions was the main focus of the study. Geochemical modelling of the eluates was used to derive a theoretical description of the underlying leaching phenomena for the carbonated material as compared to the original slag. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases, and lower-Ca/Si-ratio minerals were found to control leaching in carbonated slag eluates as compared to the corresponding untreated slag sample as a result of Ca depletion from the residual slag particles. Clear evidence was also gained of solubility control for Ca, Mg and Mn by a number of carbonate minerals, indicating a significant involvement of the original slag constituents in the carbonation process. The release of toxic metals (Zn, V, Cr, Mo) was found to be variously affected by carbonation, owing to different mechanisms including pH changes, dissolution/precipitation of carbonates as well as sorption onto reactive mineral surfaces. The leaching test results were used to derive further considerations on the expected metal release levels on the basis of specific assumptions on the relevant pH domains for the untreated and carbonated slag.

Effect of ultrasonication on anaerobic degradability of solid waste digestate.

This paper evaluates the effect of ultrasonication on anaerobic biodegradability of lignocellulosic residues. While ultrasonication has been commonly applied as a pre-treatment of the feed substrate, in the present study a non-conventional process configuration based on recirculation of sonicated digestate to the biological reactor was evaluated at the lab-scale. Sonication tests were carried out at different applied energies ranging between 500 and 50,000kJ/kg TS. Batch anaerobic digestion tests were performed on samples prepared by mixing sonicated and untreated substrate at two different ratios (25:75 and 75:25 w/w). The results showed that when applied as a post-treatment of digestate, ultrasonication can positively affect the yield of anaerobic digestion, mainly due to the dissolution effect of complex organic molecules that have not been hydrolyzed by biological degradation. A good correlation was found between the CH4 production yield and the amount of soluble organic matter at the start of digestion tests. The maximum gain in biogas production was 30% compared to that attained with the unsonicated substrate, which was tentatively related to the type and concentration of the metabolic products.

Effects of thin-film accelerated carbonation on steel slag leaching.

This paper discusses the effects of accelerated carbonation on the leaching behaviour of two types of stainless steel slags (electric arc furnace and argon oxygen decarburisation slag). The release of major elements and toxic metals both at the natural pH and at varying pH conditions was addressed. Geochemical modelling of the eluates was used to theoretically describe leaching and derive information about mineralogical changes induced by carbonation. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases; geochemical modelling indicated that the Ca/Si ratio of Ca-controlling minerals shifted from ∼ 1 for the untreated slag to 0.5-0.67 for the carbonated samples, thus showing that the carbonation process left some residual Ca-depleted silicate phases while the extracted Ca precipitated in the form of carbonate minerals. For toxic metals the changes in leaching induced by carbonation appeared to be mainly related to the resulting pH changes, which were as high as ∼ 2 orders of magnitude upon carbonation. Depending on the specific shape of the respective solubility curves, the extent of leaching of toxic metals from the slag was differently affected by carbonation.

Thin-film versus slurry-phase carbonation of steel slag: CO2 uptake and effects on mineralogy.

The results of direct aqueous accelerated carbonation of three types of steel manufacturing residues, including an electric arc furnace (EAF) slag and two basic oxygen furnace (BOF) slags, are reported. Batch accelerated carbonation tests were conducted at different temperatures and CO2 pressures applying the thin-film route (liquid to solid, L/S, ratio=0.3L/kg) or the slurry-phase route (L/S ratio=5L/kg). The CO2 uptake strongly depended on both the slag characteristics and the process route; maximum yields of 280 (EAF), 325 (BOF1) and 403 (BOF2) gCO2/kg slag were achieved in slurry phase at T=100°C and pCO2=10 bar. Differently from previous studies, additional carbonates (other than Ca-based phases) were retrieved in the carbonated BOF slags, indicating that also Mg-, Fe- and Mn-containing phases partially reacted with CO2 under the tested conditions. The results hence show that the effects of accelerated carbonation in terms of CO2 uptake capacity, yield of mineral conversion into carbonates and mineralogy of the treated product, strongly rely on several factors. These include, above all, the mineralogy of the original material and the operating conditions adopted, which thus need specific case-by-case optimization to maximize the CO2 sequestration yield.

Determination of beta 2-agonists in hair by gas chromatography/mass spectrometry.

A method is described for the determination of the beta 2-agonists clenbuterol and salbutamol in hair. The method involves washing hair in sodium dodecyl hydrogensulphate solution, chemical digestion of the hair matrix in alkaline medium, solid-phase extraction, derivatization with methylboronic acid and analysis by gas chromatography/electron impact mass spectrometry in either the selected-ion monitoring or the scan mode. the effects of chemical digestion and of extraction on the recovery of the analytes were evaluated. Derivatization with methyl-boronic acid was compared with trimethylsilylation for GC/MS analysis of hair extracts, and was found to give mass spectra which showed more structural information with less chemical noise and better sensitivity. The proposed method was tested on real hair samples obtained from guinea pigs treated with growth-promoting doses of clenbuterol and salbutamol. Both compounds could be detected in hair of treated animals.

Hyphenation of coupled-column liquid chromatography and thermospray tandem mass spectrometry for the rapid determination of beta 2-agonist residues in bovine urine using direct large-volume sample injection. Set-up of single-residue methods for clenbuterol and salbutamol.

In a previous work, coupled-column LC (LC/LC) with direct large-volume sample injection for the analysis of beta 2-agonists in bovine urine was investigated, in view of its combination with thermospray (TSP) tandem mass spectrometric (MS/MS) detection. In this work, the potential of both conventional LC and LC/LC coupled to TSP-MS/MS for the rapid determination of beta 2-agonists in bovine urine was evaluated. It was first established that, in order to avoid disturbances in TSP-MS/MS detection due to changes in pressure and flow rate of the mobile phase, LC/LC is preferable to conventional LC. Then, selecting clenbuterol and salbutamol as model compounds for the class of beta 2-agonists, two single-residue LC/LC/TSP-MS/MS methods were developed, permitting the determination of the analytes in bovine urine samples with a limit of quantification of at least 0.1 ng, ml-1, with a sample throughput of 4 h-1. The methods were validated by analysing both spiked urine samples and samples containing clenbuterol or salbutamol residues. Mean recoveries from urine samples spiked with clenbuterol at levels of 5 and 0.22 ng ml-1 were 107% (n = 9, RSD = 7.4%) and 102% (n = 6, RSD = 14%), respectively. A bovine urine sample containing 1.28 ng ml-1 clenbuterol residue (previously quantified by GC/MS) was re-analysed by LC/LC/TSP-MS/MS on four different days (n = 3, each day) and yielded a mean concentration of 1.31 ng ml-1, with a reproducibility of 8.4%. Bovine urine samples spiked with salbutamol at levels of 10.8 and 0.55 ng ml-1 yielded mean recoveries of 101% (n = 3, RSD = 1%) and 89% (n = 3, RSD = 13%), respectively. In bovine urine samples containing salbutamol residues, the concentrations of unconjugated salbutamol were found to be in the range 8-57 ng ml-1.

Rapid and highly selective GC/MS/MS detection of heroin and its metabolites in hair.

A direct treatment of methanol-washed hair with a silylating solution is proposed to extract heroin, O-6-monoacetylmorphine, morphine, acetylcodeine, and codeine, obtaining the simultaneous derivatization of the hydroxylated metabolites and reducing potential sample contamination. Analysis is performed by capillary gas chromatography-tandem mass spectrometry (GC/MS/MS) using multiple selected reaction monitoring. Owing to the selectivity and sensitivity of the GC/MS/MS analysis, and to the extremely simple treatment of the sample, the method fulfils the requirements of both clinical and forensic diagnosis of heroin use.

A fatal case of poisoning with cantharidin.

A case of fatal poisoning due to voluntary ingestion of cantharides powder for aphrodisiac purposes is reported. Clinical history, autopsy and analytical findings are described. Blood and urine samples collected during the 30 h of survival, as well as the cantharides product, were analyzed by gas chromatography-mass spectrometry. On the basis of the percentage of the active principle measured in the powder, an ingested dose of 26-45 mg of cantharidin could be estimated.

Determination of opiates in hair. Effects of extraction methods on recovery and on stability of analytes.

In order to evaluate (i) the recovery of extraction of opiates from authentic hair samples and (ii) the extent of hydrolysis of acetylated opiates (6-acetylmorphine, acetylcodeine) occurring during sample preparation, three different methods of extraction commonly used for opiates have been compared. To this purpose a sample consisting of a pool of hair collected from several heroin overdose cases has been submitted alternately to (A) digestion in 2 M NaOH at 80 degrees C for 1 h (n = 5), (B) incubation in 0.1 M HCl at 45 degrees C for 18 h (n = 5) and (C) incubation in methanol at 37 degrees C for 18 h (n = 5). After pH adjustment of the different incubation media to 7-8, analytes have been isolated by means of SPE using Bond Elut certify columns and derivatized with MSTFA. Analyses have been performed by either GC-MS in the selected ion monitoring mode or, omitting SPE, by radioimmunoassay. The extent of hydrolysis of 6-acetylmorphine to morphine and of acetylcodeine to codeine have been determined by submitting blank hair samples spiked with the acetylated analytes to the different extraction methods and measuring the amount of morphine and codeine formed. Both the recovery of extraction of the total morphine fraction (6-acetylmorphine + morphine) and the rate of hydrolysis of 6-acetylmorphine were found to be in the order: A > B > C. Similar results were obtained for the total codeine fraction (acetylcodeine + codeine). These results clearly indicate that: (i) the concentration of opiates measured in hair depends on the extraction method used; (ii) ratios between different analytes (e.g. 6-acetylmorphine vs. morphine) may reflect the rate of hydrolysis during sample preparation rather than different types of exposure to opiates.

Simultaneous hair testing for opiates, cocaine, and metabolites by GC-MS: a survey of applicants for driving licenses with a history of drug use.

A sensitive GC-MS method for the simultaneous determination of opiates, cocaine, and metabolites in hair at a cut-off level of 0.1 ng/mg was adopted to assess past exposure to these drugs in applicants for driving licenses with a history of drug use. The sampling protocol consisted of collection of one hair (sample A, 5-cm length) and one urine sample. When hair and urine (EMIT Syva, cut-off levels: 0.3 mg/l for opiates, 0.15 mg/l for cocaine, GC-MS confirmation of positives) were both positive or negative the protocol was concluded. In the other cases, the assessment of 'current exposure' to drugs was carried out, in order to avoid seriated random urinalysis, by collecting a second hair sample (sample B) 6 weeks later and analysing the proximal 1-cm segment. Out of the 214 'A' hair samples analyzed, 14 (6.5%) tested positive for morphine and/or 6-acetylmorphine (6AM), and 26 (12%) for cocaine and/or benzoylecgonine (BE), whereas none of the samples tested positive for both drugs. Levels between 0.1 and 1 ng/mg of the single analytes were found in eight out of the 14 morphine-6AM positives (57%) and in 18 out of the 26 cocaine-BE positives (69%). The time course of positive cases showed a progressive decrease of morphine-6AM positives and a corresponding increase of cocaine-BE positives within the study period September 1995-February 1999. No cases with positive urine and negative hair were observed. Among the 40 positive cases, seven (four and three for opiates and cocaine, respectively) were found to be 'currently exposed to drug', four by urinalysis (three and one) and three by analysis of the hair sample B (1 and 2).

Hair analysis for opiates, cocaine and metabolites. Evaluation of a method by interlaboratory comparison.

The aim of this study was to evaluate the performance of a technique for the simultaneous testing of opiates, cocaine and metabolites in hair by interlaboratory comparison. Sixteen forensic and clinical laboratories with different degrees of experience in hair analysis participated voluntarily in the study (no selection criteria were applied). The suggested analytical procedure, the one routinely used in our laboratory, consisted of incubation in HCl 0.1N (45 degrees C, overnight), solid phase extraction (with Bond Elut Certify) cartridges), derivatisation (trimethylsilyl (TMS) derivatives) and GC-MS analysis. Three different mixtures of finely cut (1 mm or less) hair were prepared using drug-users' and drug-free hair: one 'negative' sample (<0.1 ng/mg for morphine, 6-acetylmorphine (6AM), cocaine and benzoylecgonine (BE)), one 'low concentration' sample (between 0.5 and 2 ng/mg) and one 'high concentration' sample (>3 ng/mg). Accuracy and precision (CV% lower than 5.1, 9.9, 5.2, 3.8, 7.3 and 8.3% for morphine, 6AM, codeine, cocaine, BE, and methylecgonine (ME), respectively; range 0.5-5 ng/mg) of the method and homogeneity of the mixtures were evaluated in our laboratory by intraday (CV% lower than 12% for all analytes) and interday analyses (CV% lower than 17% for all analytes except 6AM, 25%). Participants in the study were grouped into: (1) laboratories (n = 6) obtaining the best qualitative and quantitative values, corresponding to those with long experience in hair analysis; (2) laboratories (n = 5) with no reported false positive and/or false negatives; (3) laboratories (n = 5) with one or more reported false positives/false negatives. The results obtained by the labs of the first group were used as reference values. The scatter of data was similar to those obtained in other published studies.

Engineering and environmental properties of thermally treated mixtures containing MSWI fly ash and low-cost additives.

An experimental work was carried out to investigate the feasibility of application of a sintering process to mixtures composed of Municipal Solid Waste Incinerator (MSWI) fly ash and low-cost additives (waste from feldspar production and cullet). The proportions of the three constituents were varied to adjust the mixture compositions to within the optimal range for sintering. The material was compacted in cylindrical specimens and treated at 1100 and 1150 degrees C for 30 and 60 min. Engineering and environmental characteristics including weight loss, dimensional changes, density, open porosity, mechanical strength, chemical stability and leaching behavior were determined for the treated material, allowing the relationship between the degree of sintering and both mixture composition and treatment conditions to be singled out. Mineralogical analyses detected the presence of neo-formation minerals from the pyroxene group. Estimation of the extent of metal loss from the samples indicated that the potential for volatilization of species of Pb, Cd and Zn is still a matter of major concern when dealing with thermal treatment of incinerator ash.