Kinetics of the tropospheric formaldehyde loss onto mineral dust and urban surfaces

The kinetics of the heterogeneous reaction between gaseous HCHO and TiO₂/SiO₂ mineral coatings were investigated using a coated-wall flow tube to mimic HCHO loss on mineral aerosol and TiO₂ coated depolluting urban surfaces. The measured uptake kinetics were strongly enhanced when the flow tube was irradiated with 340–420 nm UV light with an irradiance of 1.45 mW cm^?2. The associated BET uptake coefficients ranged from (3.00 ± 0.45) × 10^?9 to (2.26 ± 0.34) × 10^?6 and were strongly dependent on HCHO initial concentration, relative humidity, temperature, and TiO₂ content in the mineral coating, which ranged from 3.5 to 32.5 ppbv, 6–70%, 278–303 K, and 1–100 %wt, respectively. The measured kinetics were well described using a Langmuir–Hinshelwood type formalism. The estimated uptake coefficients were used to discuss the importance of heterogeneous HCHO surface loss, in terms of deposition lifetimes, as compared to major homogeneous gas-phase losses such as OH reaction and photolysis. It is found that deposition may compete with gas-phase removal of HCHO in a dense urban environment if more than 10% of the urban surface is covered with TiO₂ treated material.     

Fate and degradation of triasulfuron in soil and water under laboratory conditions

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.     

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Minimization of the environmental impact in the unhairing of bovine hides

This study tests an alternative method to the traditional unhairing method used during the process of tanning the hides. The new method is based on the substitution of sodium sulfide by hydrogen peroxide as an unhairing agent in both hair recovery and recirculation of the floats employed in the process. The properties of the hides obtained using the two methods have been compared and the results indicate that those hides have similar physical, chemical, and organoleptic properties. However, the differences existing from an environmental point of view are significant. These include reductions of water consumption (approx 70%), chemical oxygen demand (approx 35%), toxicity (98%) and total kjendhal nitrogen (50%). Also, the risk associated with the production of hydrogen sulfide is eliminated, which implies a great improvement in terms of safety for the workers. Given the large amounts of water and chemical pollution discharged in the process, the reductions in absolute values represent a significant improvement. A financial assessment was carried out to demonstrate that the proposed new system is 16% more economic than the traditional one.     

Use of electrochemical technology to increase the quality of the effluents of bio-oxidation processes. A case studied

In this work, it has been studied the use of conductive-diamond electrochemical oxidation (CDEO) as a refining technology to assure the quality of the effluents of door manufacturing processes (DMP). To do this, the raw effluents of these factories have been treated by a combination of physicochemical, biological and CDEO treatments. CDEO was found to be a feasible alternative to the refinement of a wooden DMP waste. It can successfully decrease the organic load of the effluents of the biological oxidation with low energy requirements. In addition, in case of incidents in the biological process, CDEO can treat successfully the effluents of the coagulation process. The effluents of the biological treatment have also been treated by CDEO in order to check the possible use of electrochemical technology to increase the biodegradability of the effluents and their possible recycle to the biological treatment. Unfortunately, electrochemical technology was found to be not adequate to increase the biodegradability of the effluents of a biological treatment. The hard oxidation conditions generated during CDEO do not lead to the accumulation of intermediates but to the almost direct formation of carbon dioxide. Lowering the current density or changing the electrodes can not enhance the biodegradability of the effluents of an electrochemical cell.     

Long-term development of inorganic nutrients and chlorophyll alpha in the open northern Baltic Sea

Eutrophication is an ongoing process in most parts of the Baltic Sea. This article reports on the changes during recent decades of several eutrophication-related variables in the open sea areas surrounding Finland (wintertime nutrient concentrations, wintertime nutrient ratios, and summer time chlorophyll alpha concentrations at the surface). The sum of nitrate- and nitrite-nitrogen ([NO3+NO2]-N) was observed to increase nearly fourfold in the Northern Baltic Proper and the Gulf of Finland and almost double in the Bothnian Sea from the 1960s until the 1980s or 1990s. The increase was followed by a decrease, which was modest in the two former subregions. Phosphate-phosphorus (PO4-P) concentrations followed a similar pattern in the Northern Baltic Proper (threefold increase and subsequent slight decrease) and Bothnian Sea (30% increase and subsequent decrease), but increased throughout the study in the Gulf of Finland, with the present concentration being threefold to the measurements made in the early 1970s. The PO4-P concentration decreased throughout the study in the Bothnian Bay. Silicate-silicon (SiO4-Si) concentrations decreased 30-50% from the early 1970s to the late 1990s and increased 20-40% thereafter in the Northern Baltic Proper, the Gulf of Finland, and the Bothnian Sea. Chlorophyll alpha showed an increase of over 150% in the Northern Baltic Proper and the Gulf of Finland from the 1970s until the early 2000s. In the Bothnian Sea the chlorophyll alpha concentration increased more than 180% from the late 1970s until the late 1990s, and decreased thereafter. According to these long-term observations, the Gulf of Finland and Northern Baltic Proper show clear signs of eutrophication, which may be emphasized by hydrographical changes affecting the phytoplankton communities and thus the algal biomass.     

Characterisation of a reference site for quantifying uncertainties related to soil sampling

The paper reports a methodology adopted to face problems related to quality assurance in soil sampling. The SOILSAMP project, funded by the Environmental Protection Agency of Italy (APAT), is aimed at (i) establishing protocols for soil sampling in different environments; (ii) assessing uncertainties associated with different soil sampling methods in order to select the "fit-for-purpose" method; (iii) qualifying, in term of trace elements spatial variability, a reference site for national and international inter-comparison exercises. Preliminary results and considerations are illustrated.     

Enhanced resistance of yeast mutants deficient in low-affinity iron and zinc transporters to stannous-induced toxicity

Tin or stannous (Sn²⁺) compounds are used as catalysts, stabilizers in plastic industries, wood preservatives, agricultural biocides and nuclear medicine. In order to verify the Sn²⁺ up-take and toxicity in yeast cells we utilized a multi-elemental analysis known as particle-induced X-ray emission (PIXE) along with cell survival assays and quantitative real-time PCR. The detection of Sn²⁺ by PIXE was possible only in yeast cells in stationary phase of growth (STAT cells) that survive at 25 mM Sn²⁺ concentration. Yeast cells in exponential phase of growth (LOG cells) tolerate only micro-molar Sn²⁺ concentrations that result in intracellular concentration below of the method detection limit. Our PIXE analysis showed that STAT XV185-14c yeast cells demonstrate a significant loss of intracellular elements such as Mg, Zn, S, Fe and an increase in P levels after 1 h exposure to SnCl₂. The survival assay showed enhanced tolerance of LOG yeast cells lacking the low-affinity iron and zinc transporters to stannous treatment, suggesting the possible involvement in Sn²⁺ uptake. Moreover, our qRT-PCR data showed that Sn²⁺ treatment could generate reactive oxygen species as it induces activation of many stress-response genes, including SOD1, YAP1, and APN1.     

Chlorinated and brominated organic contaminants in fish from Shanghai markets: a case study of human exposure

In the present study were two favorite edible fish species for local residents, i.e., mandarin fish and crawfish, collected from the Shanghai market and analyzed for selected organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), hexabromocyclododecane (HBCDD), polybrominated diphenyl ethers (PBDEs) and methoxylated PBDEs (MeO-PBDEs). Efforts were also made to identify the potential sources of these contaminants. Comparable concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and HBCDD were found in muscle tissue of mandarin fish from Guangdong (GDF), the Pearl River Delta and from Taihu Lake (TLF), the Yangtze River Delta. Levels of chlordanes, PCBs and PBDEs were about one magnitude lower in TLF compared to GDF. The concentrations of OCPs in the butter-like gland of the crawfish (CFB) were 2-5 times of those in the crawfish muscle (CFM) while concentrations of PCBs, PBDEs and MeO-PBDEs were comparable. The different patterns and levels of chlorinated and brominated organohalogen contaminants seen in mandarin fish from GDF and TLF indicates that different types of chemicals might be used in the two delta regions. The present study also shows a good correlation between the concentrations of hexachlorobenzene (HCB) and pentachloroanisol (PCA) in fish for the first time. Fish consumption limits based on chemical contaminants with non-carcinogenic effects were calculated. The estimated maximum daily consumption limit for GDF, TLF, CFM and CFB were 1.5, 2.6, 3.7 and 0.08 kg, respectively, indicating no significant risk regarding the persistent organic pollutants measured in the present study.