Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

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.     

Mortality due to haematological cancer in cities close to petroleum refineries in Spain

Controversy exists as to whether working or living in the vicinity of a petroleum refinery (RF) increases the risk of haematological cancer (HC). The European Pollutant Release and Transfer Register obliges petroleum refineries to notify their emissions of toxic substances which include carcinogenic substances. Our objective is to determine if living in the proximity of an RF is associated with a greater risk of mortality due to HC in the census tracts (CTs) of the Spanish cities of Bilbao, Cartagena, Castellón, La Coruña, Huelva, and Santa Cruz de Tenerife. This is an ecological study of mortality in the years 1996–2007 which includes 968 CTs with 1,263,371 inhabitants. Exposure has been measured as the distance from the centroid of each CT to the RF. The Besag–York–Mollié autoregressive spatial model has been fitted by R-INLA to estimate the relative risk (RR) and 95 % credible intervals (95 % CrI) for distance in quintiles. The most distant quintile has been taken as the reference. A total of 2,574 persons died of HC. The distances from the CTs to RFs ranged from 0.5 to 22.5 km (median?=?7.6 km). All of the RRs for the quintiles of distances in Huelva were greater than 1. Statistically significant excess risk was shown in Cartagena in the nearest CT (1.8 to 6.8 km; RR?=?1.43, 95 % CrI 1.02 to 2.02). Radial effects have not been detected between the CT of residence and the petroleum RF in mortality due to HC in any of the cities.     

Complex genetic structure of a euryhaline marine fish in temporarily open/closed estuaries from the wider Gulf of Aden

Temporarily open/closed estuaries (TOCEs) are major ecosystems of the Indian Ocean coastal zones. Their functioning is tightly linked to climatic events such as monsoons and storms, and their mouth can close up for prolonged and variable periods of time, thus limiting their connectivity with the marine environment. Two types of genetic markers (i.e., mitochondrial cytochrome c oxidase I (COI) gene and microsatellites) were used to assess the genetic structure of 288 individuals of Terapon jarbua, a widely distributed fish species in the wider Gulf of Aden. Firstly, the hypothesis of panmixia was tested. Then, alternative hypotheses were investigated to explain the population genetic structure of T. jarbua: could it be shaped by (1) regional biogeographic barriers (i.e., Socotra Island vs. mainland Yemen) and/or (2) the particular functioning of TOCEs in relation to the species life cycle and particular physical ocean parameters? On one hand, the polymorphism of the COI inferred (1) a high haplotype diversity and a reduced nucleotide diversity over the whole data set and (2) a “star-like” shape of the haplotype network, thus suggesting a population expansion after local extinctions during the Pleistocene glaciations. On a second hand, the genotyping of eight microsatellites showed a significant genetic differentiation between T. jarbua populations in the wider Gulf of Aden (F _ST = 0.035, p < 0.01), and thus, the panmixia hypothesis was rejected. Analyses of molecular variance results did not show any significant structure between Socotra Island and mainland Yemen and thus did not support the role of biogeographic barriers in structuring T. jarbua populations. Significant multi-locus deficits in heterozygotes at particular locations displaying high levels of F _IS were recorded. It was suggested that a possible Wahlund effect took place in those TOCEs which could gather several cohorts of larvae stemming from different marine subpopulations over the sampled area. The present study emphasized the uniqueness of each TOCE as a potential reservoir of biodiversity and the urgent need for a better conservation program of those estuaries in the region, in order to avoid habitat fragmentation and permanent closure of those nursery areas by human activities.