One of the most serious externalities of agricultural activity relates to greenhouse gas emissions. This work tests this relationship for the Portuguese case by examining data compiled since 1961. Employing cointegration techniques and vector error correction models (VECMs), we conclude that the evolution of the most representative vegetables and fruits in Portuguese production are associated with higher controls on the evolution of greenhouse gas emissions. Reversely, the evolution of the output levels of livestock and the most representative animal production have significantly increased the level of CO₂ (carbon dioxide) reported in Portugal. We also analyze the cycle length of the long-term relationship between agricultural activity and greenhouse gas emissions. In particular, we highlight the case of synthetic fertilizers, whose values of CO₂ have quickly risen due to changes in Portuguese vegetables, fruit, and animal production levels.

This paper reanalyzes the determinants of the CO₂ emissions in France. For this purpose, it considers the unit root test with two structural breaks and a dynamic ordinary least squares estimation. The paper also considers the effects of the energy consumption and the economic complexity on CO₂ emissions. First, it is observed that the EKC hypothesis is valid in France. Second, the positive effect of the energy consumption on CO₂ emissions is obtained. Third, it is observed that a higher economic complexity suppresses the level of CO₂ emissions in the long run. The findings imply noteworthy environmental policy implications to decrease the level of CO₂ emissions in France.

Cyanate and its derivatives are considered as environmental hazardous materials. Cyanate is released to the environment through many chemical industries and mining wastewater. Cyanase enzyme converts cyanate into CO₂ and NH₃ in a bicarbonate-dependent reaction. At low cyanate concentrations, the endogenous plant cyanases play a vital role in cyanate detoxification. However, such cyanate biodegradation system is probably insufficient due to the excess cyanate concentrations at contaminated sites. In this study, we have transferred the activity of the cyanobacterial cyanase into Arabidopsis thaliana plants in order to enhance plant resistance against cyanate toxicity. The enzyme was shown to be active in planta. Transgenic plants exposed to cyanate, either applied by foliar spray or supplemented in growth medium, showed less reduction in pigment contents, antioxidant enzymes, carbohydrate contents, and reduced levels of plant growth retardation. Plant growth assays under cyanate stress showed enhanced growth and biomass accumulation in cyanase overexpressors compared to control plants. Results of this study provide evidence for developing novel eco-friendly phytoremediation systems for cyanate detoxification.

In this study, the white-rot fungus Cyathus bulleri was cultivated on low-cost agro-residues, namely wheat bran (WB), wheat straw (WS), and domestic waste orange peel (OP) for production of ligninolytic enzymes. Of the three substrates, WB and OP served as good materials for the production of laccase with no requirement of additional carbon or nitrogen source. Specific laccase activity of 94.4 U mg⁻¹ extracellular protein and 21.01 U mg⁻¹ protein was obtained on WB and OP, respectively. Maximum decolorization rate of 13.6 μmol h⁻¹ U⁻¹ laccase for reactive black 5 and 22.68 μmol h⁻¹ U⁻¹ laccase for reactive orange 16 (RO) was obtained with the WB culture filtrate, and 11.7 μmol h⁻¹ U⁻¹ laccase for reactive violet 5 was observed with OP culture filtrate. Importantly, Kiton blue A (KB), reported not to be amenable to enzymatic degradation, was degraded by culture filtrate borne activities. Products of degradation of KB and RO were identified by mass spectrometry, and a pathway of degradation proposed. WB-grown culture filtrate decolorized and detoxified real and simulated textile effluents by about 40%. The study highlights the use of inexpensive materials for the production of enzymes effective on dyes and effluents.

In this work, mesoporous silica mobil composition of matter no. 41 (MCM-41) was synthesized by the sol-gel method. Two different surface modifications were made to transform this material into a very active adsorbent and catalyst support: (i) impregnation of iron nanoparticles and (ii) hydrophobization via chemical vapor deposition (CVD) with ethanol. The materials prepared with different iron contents, i.e., 2.5, 5, and 10 %, after hydrophobization, were characterized by several techniques. CHN analysis and Raman spectroscopy proved that approximately 15 % of carbon is deposited during CVD process mainly as organized carbonaceous structures. The specific surface area was determined by the BET method as up to 1080 m² g⁻¹, which explains the excellent results of the materials in the adsorption of model dyes methylene blue and indigo carmine. Mössbauer spectroscopy, thermogravimetric (TG)/DTG analysis, and transmission electron microscopy (TEM) images showed that the iron supported may be partially reduced during the CVD process to Fe²⁺ species, which are stabilized by the carbon coating. This iron species plays an important role in the oxidation of different contaminants, such as quinoline and methylene blue. The results obtained in the catalytic tests showed to be very promising.

The role of different operational parameters related to Fenton reactions (pH, concentration of Fe²⁺ and H₂O₂, and reaction time) and of Cl⁻ and SO ₄ ⁻ was investigated in the degradation of the azo dye Direct Red 81, expressed in terms of its decolorization. The factorial design and Pareto’s charts showed that only Fe²⁺ concentration and pH influence the decolorization under the conditions evaluated. So, only these parameters were optimized using the response surface model. Under the best experimental conditions (initial pH 2.5, 11 mg L⁻¹ Fe²⁺, 78 mg L⁻¹ H₂O₂, and 20 min of reaction), 94 % of decolorization was achieved. However, even under the these conditions, but in the presence of Cl⁻ and SO ₄ ⁻ , a striking loss of efficiency was observed as the concentration of these ions was increased, due the formation of chloride- and sulfate-iron complexes and less reactive inorganic radicals (Cl₂ •– and SO₄ •–). The results show that the presence of Cl⁻ is more deleterious, since sulfate-iron complexes are more reactive towards H₂O₂, and the SO₄ •– turns out to favor the degradation. On the other hand, the negative effect of Cl⁻ can be compensated by increasing the chloride concentration up to 300 mmol L⁻¹. In addition, although a high degradation level has been obtained by monitoring the dye absorbance and by HPLC-UV, a low mineralization occurred, being generated degradation products of higher ecotoxicity to Vibrio fischeri, showing the need of subsequent studies to identify these compounds as well as the application of additional treatments aiming the complete mineralization of the dye.

Gaseous and particulate emissions from a ship diesel research engine were elaborately analysed by a large assembly of measurement techniques. Applied methods comprised of offline and online approaches, yielding averaged chemical and physical data as well as time-resolved trends of combustion by-products. The engine was driven by two different fuels, a commonly used heavy fuel oil (HFO) and a standardised diesel fuel (DF). It was operated in a standardised cycle with a duration of 2 h. Chemical characterisation of organic species and elements revealed higher concentrations as well as a larger number of detected compounds for HFO operation for both gas phase and particulate matter. A noteworthy exception was the concentration of elemental carbon, which was higher in DF exhaust aerosol. This may prove crucial for the assessment and interpretation of biological response and impact via the exposure of human lung cell cultures, which was carried out in parallel to this study. Offline and online data hinted at the fact that most organic species in the aerosol are transferred from the fuel as unburned material. This is especially distinctive at low power operation of HFO, where low volatility structures are converted to the particulate phase. The results of this study give rise to the conclusion that a mere switching to sulphur-free fuel is not sufficient as remediation measure to reduce health and environmental effects of ship emissions.

Sources of plutonium isotopes to the marine environment are well defined, both spatially and temporally which makes plutonium (Pu) a potential tracer for oceanic processes. This paper presents the optimisation and validation of an analytical procedure for ultra-trace determination of Pu isotopes (²³⁹Pu and ²⁴⁰Pu) in seawater based on the external calibration and sector field inductively coupled plasma mass spectrometry (SF ICP-MS) determination. Additionally, method for Pu isotope ratio (²⁴⁰Pu/²³⁹Pu) in marine samples is also discussed. A combination of two-step anion exchange (AG1-X8) and one-step extraction chromatography (TEVA) was very efficient resulting in uranium (U) decontamination factor of 5 × 10⁶–1 × 10⁸. A full validation approach in line with ISO 17025 standard and Eurachem guidelines was followed. With this in mind, blanks, recovery (87 ± 8 %, k = 2), within-laboratory repeatability (5.6 %), limits of detection (0.12 and 0.08 fg mL⁻¹ for ²³⁹Pu and ²⁴⁰Pu, respectively) and expanded uncertainty (13 %, k = 2) were systematically assessed. The procedure was applied for the determination of ²³⁹Pu and Pu in seawater sample coming from Mediterranean Sea. Obtained results were in good agreement with results obtained with alpha spectrometry, applied on the same seawater sample. Pu/²³⁹Pu atom ratio in seawater sample from the Mediterranean Sea was also determined. The precision and accuracy of ²⁴⁰Pu/²³⁹Pu isotopic ratio analysis were carefully examined using NBS-947 isotopic standard. ²⁴⁰Pu/²³⁹Pu ratio was found to be 0.187 ± 0.006 and is in agreement with accepted ratios for the global fallout of Pu.

Abiotic stress factors, including ultraviolet (UV) radiation, significantly affect insect life. UV-A radiation (320–400 nm) has been widely used for insect control since it increases the production of ROS and causes oxidative cell damage. In the present study, we evaluated the effects of UV-A irradiation on an important pest in China, the ear-cutting caterpillar, Mythimna separata (Lepidoptera: Noctuidae). We exposed 3-day-old M. separata adults to UV-A radiation for different periods of time (0, 30, 60, 90, and 120 min) and evaluated the resulting total antioxidant capacity and the activity of the antioxidant enzymes superoxide dismutase, catalase, peroxidase, and glutathione-S-transferase. The total antioxidant capacity significantly increased after exposure to UV-A radiation for 60 min but decreased after 90 and 120 min of exposure, compared with the control. The antioxidant activity of glutathione-S-transferase, superoxide dismutase, catalase, and peroxidase increased after 60-min exposure, and it was decreased at the longest exposure period 120 min. The longest exposure time period relatively activates the xenobiotic detoxifying enzymes like glutathione-S-transferase, superoxide dismutase, catalase, and peroxidase enzymes. The longest duration of UV-A radiation may cooperate with pesticide detoxification mechanism in insects, making them more susceptible to insecticides. Our results demonstrated that UV irradiation causes oxidative stress, affects the activity of antioxidant enzymes, and disturbs the physiology of M. separata adults.

We assessed contamination in the Upper Tisza region (Hungary, Central Europe), analyzing the elemental concentrations in sediment cores of oxbows. Our hypothesis was that the metal contamination which occurred in the year 2000 and which came from the mining area in Transylvania (Romania) may be detected even 15 years after the contamination, based on the vertical profile of sediment cores. Sediment cores were collected from five oxbows, and the following elements were measured with microwave plasma-atomic emission spectrometry (MP-AES): Cu, Cr, Ba, Fe, Mn, Pb, Sr, and Zn. Among the oxbows studied, there was one protected oxbow, three were used for fishing, and one was contaminated with sewage. Our results indicated that the year of contamination is still observable in the vertical profile of the sediment cores. The pollution index (PI) was used to characterize the sediment enrichment of metal elements in the sediment cores. In the case of Cu, Pb, and Zn, the contamination which originated in the year 2000 was detected in the layers of the sediment cores. The contamination levels of Cu, Pb, and Zn were high or moderate in the studied oxbows. All oxbows were moderately contaminated by Mn, while a moderate level of contamination was found for Fe in the protected oxbow, one fishing oxbow, and the sewage-contaminated oxbow. In the fishing oxbows, a low level of contamination was found for Fe. The contamination level of Sr was low in the protected oxbow and in the two fishing oxbows, while in one of the fishing oxbows and in the sewage-contaminated oxbow, a moderate level of Sr contamination was found. The pollution index scores indicated that the contamination level for Ba and Cr was low in the sediment cores of the oxbows studied. Our results indicated that the contamination of the Tisza River from the mining area in Northern Romania has been continuous and is still ongoing.