Electrochemical advanced oxidation processes: today and tomorrow. A review

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical (^?OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which ^?OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which ^?OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.     

Long-term effects on nitrogen and benthic fauna of extreme weather events: Examples from two Swedish headwater streams

Climate change is expected to cause an increased frequency of extreme events such as heavy floods and major storms. Such stochastic events have an immediate impact on surface water quality, but the long-term effects are largely unknown. In this study, we assess long-term monitoring data from two Swedish headwater catchments affected by extreme weather events. At one site, where nitrogen effects in soil water, groundwater, and stream water were studied after storm-felling and subsequent forest dieback from bark beetle attack, long-term (>5 years) but relatively modest (generally <1 mg L^?1) increases in ammonium (NH₄-N) and nitrate (NO₃-N) concentrations were observed in the various aqueous media. At the other site, where effects on benthic fauna were studied in a stream impacted by extreme geophysical disturbances caused by rainstorm-induced flashflood, only short-term (1 year) effects were revealed both regarding diversity and composition of species.     

Reduction of Baltic Sea Nutrient Inputs and Allocation of Abatement Costs Within the Baltic Sea Catchment

The Baltic Sea Action Plan (BSAP) requires tools to simulate effects and costs of various nutrient abatement strategies. Hierarchically connected databases and models of the entire catchment have been created to allow decision makers to view scenarios via the decision support system NEST. Increased intensity in agriculture in transient countries would result in increased nutrient loads to the Baltic Sea, particularly from Poland, the Baltic States, and Russia. Nutrient retentions are high, which means that the nutrient reduction goals of 135 000 tons N and 15 000 tons P, as formulated in the BSAP from 2007, correspond to a reduction in nutrient loadings to watersheds by 675 000 tons N and 158 000 tons P. A cost-minimization model was used to allocate nutrient reductions to measures and countries where the costs for reducing loads are low. The minimum annual cost to meet BSAP basin targets is estimated to 4.7 billion €.     

Formation of indoor nitrous acid (HONO) by light-induced NO<Subscript>2</Subscript> heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO₂) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO₂ levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO₂ with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO₂ with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m^?2), an increase of HONO production rate of up to 8.6?·?10⁹ molecules cm^?2 s^?1 was observed at [NO₂]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m^?2), the HONO production rate increased to 2.1?·?10¹⁰ molecules cm^?2 s^?1. A high NO₂ to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO₂ heterogeneous reactions.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Degree of phosphorus saturation of an Oxisol amended with biosolids in a long-term field experiment

When applied to agricultural soils, phosphate fertilizers and the mineral or organic compounds present in solid and/or liquid waste may raise phosphorus (P) content and increase soil P saturation. The degree of phosphorus saturation (DPS) is a good indicator of potential P loss from agricultural soils. The purpose of this study was to calculate the DPS of samples from an Oxisol amended for 5 years with biosolids and mineral fertilizer. DPS was calculated based on P, iron, and aluminum extracted by ammonium oxalate and oxalic acid (DPS_ox) or by Mehlich-1 solution (DPS_M1). Treatments included NPK mineral fertilization (175 kg ha^?1 of P), B1?=?19.02 t ha^?1 of biosolids (350 kg ha^?1 of P), B2?=?38.17 t ha^?1 of biosolids (703 kg ha^?1 of P), B3?=?76.26 t ha^–1 of biosolids (1,405 kg ha^?1 of P), and a control (no P added). Water-extractable P (WEP) was also measured. Critical levels of DPS_ox and DPS_M1 (21 and 24 %, respectively) were only achieved in the topsoil (0–0.1 m) at the highest biosolid dose. Concentration of WEP was positively correlated to DPS_ox and DPS_M1. The DPS_M1 method may be an alternative to DPS_ox for assessing the environmental risk of P loss from soil into surface runoff.     

Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Evaluation of B. subtilis SPB1 biosurfactants' potency for diesel-contaminated soil washing: optimization of oil desorption using Taguchi design

Low solubility of certain hydrophobic soil contaminants limits remediation process. Surface-active compounds can improve the solubility and removal of hydrophobic compounds from contaminated soils and, consequently, their biodegradation. Hence, this paper aims to study desorption efficiency of oil from soil of SPB1 lipopeptide biosurfactant. The effect of different physicochemical parameters on desorption potency was assessed. Taguchi experimental design method was applied in order to enhance the desorption capacity and establish the best washing parameters. Mobilization potency was compared to those of chemical surfactants under the newly defined conditions. Better desorption capacity was obtained using 0.1 % biosurfacatnt solution and the mobilization potency shows great tolerance to acidic and alkaline pH values and salinity. Results show an optimum value of oil removal from diesel-contaminated soil of about 87 %. The optimum washing conditions for surfactant solution volume, biosurfactant concentration, agitation speed, temperature, and time were found to be 12 ml/g of soil, 0.1 % biosurfactant, 200 rpm, 30 °C, and 24 h, respectively. The obtained results were compared to those of SDS and Tween 80 at the optimal conditions described above, and the study reveals an effectiveness of SPB1 biosurfactant comparable to the reported chemical emulsifiers. (1) The obtained findings suggest (a) the competence of Bacillus subtilis biosurfactant in promoting diesel desorption from soil towards chemical surfactants and (b) the applicability of this method in decontaminating crude oil-contaminated soil and, therefore, improving bioavailability of hydrophobic compounds. (2) The obtained findings also suggest the adequacy of Taguchi design in promoting process efficiency. Our findings suggest that preoptimized desorption process using microbial-derived emulsifier can contribute significantly to enhancement of hydrophobic pollutants' bioavailability. This study can be complemented with the investigation of potential role in improving the biodegradation of the diesel adsorbed to the soil.     

Methylmercury levels and bioaccumulation in the aquatic food web of a highly mercury-contaminated reservoir

The low Ebro River basin (NE Spain) represents a particular case of chronic and long-term mercury pollution due to the presence of an industrial waste (up to 436 μg/g of Hg) coming from a chlor-alkali plant Albeit high total mercury (THg) levels have been previously described in several aquatic species from the surveyed area, methylmercury (MeHg) values in fish individuals have never been reported. Accordingly, in order to investigate bioaccumulation patterns at different levels of the aquatic food web of such polluted area, crayfish and various fish species, were analysed for THg and MeHg content. At the hot spot, THg mean values of crayfish muscle tissue and hepatopancreas were 10 and 15 times, respectively, greater than the local background level. Higher mean THg concentrations were detected in piscivorous (THg=0.848 ± 0.476 μg/g wet weight (ww); MeHg=0.672 ± 0.364 μg/g ww) than in non-piscivorous fish (THg=0.305 ± 0.163 μg/g ww; MeHg=0.278 ± 0.239 μg/g ww). Although these results indicated that THg in fish increased significantly with increasing trophic position, the percentage of the methylated form of Hg was not strongly influenced by differences in relative trophic position. This is an important finding, since the fraction of THg as MeHg in the top fish predator was unexpectedly lower than for other species of the aquatic food chain. Moreover, mean THg concentrations in piscivorous fish exceed the maximum level recommended for human consumption. From our findings, it is clear that for this specific polluted system, speciation becomes almost mandatory when risk assessment is based on MeHg, since single measurements of THg are inadequate and could lead to an over- or under-estimation of contamination levels.