Evaluation of a diode laser based photoacoustic instrument combined with preconcentration sampling for measuring surface–atmosphere exchange of ammonia with the aerodynamic gradient method

We present here a novel instrument for measuring surface–atmosphere exchange fluxes of ammonia. The instrument is the upgraded version of a recently developed near-infrared diode laser based photoacoustic ammonia concentration monitoring instrument, i.e. the original instrument is supplemented with two additional sampling lines, an appropriate gas handling system and an advanced software controlling gradient measurements. As a result of these developments, ammonia concentration can be measured simultaneously at three different heights above the ground and ammonia fluxes can be calculated from these data using the aerodynamic gradient method. The instrument operates fully automatically, requires minimal maintenance and has a temperature controlled, waterproof housing which makes it suitable for measurements even under harsh field conditions. Preliminary tests on stability and accuracy were carried out during two two-week field measurement campaigns, with the three sampling inlets being placed at the same height together with the inlet of a reference instrument. The readings of the three channels agreed well (with correlation coefficients above 0.96). Comparison to reference instruments showed good stability of the photoacoustic instrument, there was no measurable zero-drift or change in sensitivity during the tests. Flux measurements were carried out during a three-week field campaign in southern Scotland over fertilized grassland with reference to a wet-chemical AMANDA instrument in gradient configuration. Ammonia fluxes calculated from the data of the two instruments agreed well. Fluxes up to 2500 ng m^?2 s^?1 were observed after fertilization. The minimum detectable ammonia flux was calculated on the basis of “virtual ammonia fluxes”, from measurements carried out with all inlets at the same height and was found to be ±60 ng m^?2 s^?1 which ensures reliable measurements above intensively managed grasslands or agricultural fields.     

Environmental monitoring by gene expression biomarkers in Barbus graellsii: laboratory and field studies

Barbel (Barbus graellsii) is a freshwater fish used as a sentinel species in environmental monitoring programmes and ecotoxicological studies in northern Spain, particularly in the Ebro River basin, the largest freshwater resource in Spain. We developed specific primers for the quantification of CYP1A and metallothionein (MT)-1 and -2 gene expression by QRT-PCR in barbel in order to assess their suitability in biological effect monitoring of dioxin-like compounds and metals. All three genes responded as expected in laboratory tests, using model inducers. Hepatic CYP1A mRNA levels showed a twofold induction in fish injected intraperitoneally with beta-naphthoflavone, whereas MT-1 and MT-2 gene expression was strongly induced by cadmium (15- and 13-fold, respectively) and mercury (five- and eightfold). Barbel populations from different sites on the Ebro River basin showed a good correlation between the historical records of organochlorine pollution, CYP1A expression levels and EROD activity. Nevertheless, although metallothionein protein levels in the liver of wild fish correlated with hepatic levels of mercury, MT-1 and MT-2 gene expression did not correlate with the mercury content or with the concentration of metals in sediments from the sites inhabited by the fish. These results demonstrate the utility of barbel CYP1A-mRNA expression, but not that of MT-1 or MT-2, as a biomarker in field studies. The tools and protocols developed here are likely to apply to other species of the genus Barbus, with some 700 species distributed throughout most of the Old World.     

Mercury levels and liver pathology in feral fish living in the vicinity of a mercury cell chlor-alkali factory

Twenty-three barbels (Barbus graellsii), 30 bleaks (Alburnus alburnus) and 4 sediment samples were collected from four areas of the Cinca River (NE Spain), upstream and downstream of a mercury cell chlor-alkali plant. Mercury concentration in sediments downstream of the plant was about 25 times higher than the concentration upstream. Mercury levels in the muscle and liver of barbels downstream of the chlor-alkali plant were 10 and 30 times higher than those upstream. The average mercury concentration in the muscle and liver of barbels downstream of the factory was 1.48 and 1.78mg/kgw.w., with maximal concentrations of 2.43 and 3.64mg/kgw.w, respectively. Liver/muscle ratio of mercury was significantly higher in barbels sampled downstream of the factory. Bleak showed a similar pattern, with a significantly higher whole-body mercury concentration downstream of the chlor-alkali plant. Nevertheless, a progressive decrease in mercury concentration downstream of the impact area was found in bleak, but not in barbel. Histopathological analysis showed that fish downstream of the factory had significantly higher prevalence of liver pathologies (p<0.05). Although there are no specific histopathological markers of mercury exposure, barbels with the highest Hg levels in the liver also showed the most severe pathologies, and the processes found in these barbels were consistent with the pro-oxidant effect of heavy metals.     

Evaluation of the treatment efficiencies of paper mill whitewaters in terms of organic composition and toxicity

The efficiency of several lab scale treatments (aerobic, anaerobic and ozone or combination of these) was evaluated using two packaging board mill whitewaters. The effect of the different treatments on the elimination of the organic load, the chemical oxygen demand (COD) and the toxicity was tested as well as the relationship between these parameters. Biocides, phenolic compounds, surfactants, plasticiziers and wood extractives were identified in untreated and treated whitewaters by liquid chromatography coupled with mass spectrometry (LC-MS) or gas chromatography coupled with mass spectrometry (GC-MS). A strong dependency on the water type and treatment efficiency was observed, being the combination of anaerobic and aerobic treatments the best option to reduce the organic contaminants in these waters, although in some cases, the toxicity did not decrease. However, ozone as post-treatment permitted a further reduction of organic compounds, toxicity and COD.     

Decabrominated diphenyl ether in river fish and sediment samples collected downstream an industrial park

Fish, sediment and water samples from different places along the Spanish River Vero, a tributary of the Cinca River in the Ebro River basin, were collected in two different sampling campaigns, the first one during November 2004 and the second one in November 2005. The samples were collected up- and downstream from an industrial park. A total of 29 fishes, 6 sediments and 3 water samples were analyzed for polybrominated diphenyl ethers (PBDEs). Analytical work included 23 congeners, from tri- to deca-BDEs. The highest values for both sediment and fish samples were found downstream of the industrial park. High BDE-209 contamination was found in these sediment samples, with values up to 12 microg g(-1) dry weight. Moreover, BDE-209 was detected in 14 out of 15 biota samples collected downstream the industrial park, at concentration levels ranging from 20 to 707 ng g(-1) lipid weight, whereas it was not detected in samples collected upstream. These fish concentrations proved the bioavailability of BDE-209 and represented the highest deca-BDE values found in aquatic biota. The analysis of industrial effluents revealed that some industries contribute in some way to the BDE-209 contamination found in this area, but the industry focused on the polyamide polymerization is the main responsible.     

Uranium series radionuclides in surface waters from the Shu river (Kazakhstan)

The concentrations of (238)U, (234)U, (226)Ra, (210)Po and (210)Pb have been determined in surface waters collected along the course of the Shu River, lying on the border between Kazakhstan and Kyrgyzstan. In the study area, the river runs through some of the largest uranium deposits worldwide, which were actively exploited during the nuclear weapons and nuclear energy programmes of the former Soviet Union. The data show an increasing trend in uranium concentrations downstream the river from the city of Tokmak to the city of Shu, with good correlation between total uranium concentrations and total dissolved solids. Data on uranium isotopes disequilibrium show the presence of technogenic uranium inputs into the Shu River downstream from the city of Karasu, evidenced by a decrease in the measured (234)U/(238)U isotopic ratio from 1.63 in uncontaminated sites to 1.29 in sites affected by past mining activities.     

Ecotoxicity and genotoxicity assessment of exhaust particulates from diesel-powered buses

Diesel exhaust is one of the major sources of fine and ultra-fine particulate matter in urban air. Toxicity of diesel-powered engine emissions has been quite widely assessed; however, much less information is available on their ecotoxicity. In our study, the kinetic version of the Vibrio fischeri bioluminescence inhibition bioassay based on the ISO 21338:2010 standard was used to characterise the ecotoxicity of diesel-powered buses. It is a direct contact test in which solid samples are tested in suspension and test organisms are in direct contact with toxic particles. The age of the selected buses fell into a wide range; the oldest one was produced in 1987. Diesel engines of different emission standards (Euro0–Euro4) were included. Measured EC₅₀ values of Euro0–Euro1 engine emissions fell into the same range, 1.24–0.96 μg ml^?1, respectively. On the contrary, emission of Euro4 vehicle proved to be non-toxic. Genotoxic potential of the samples was also estimated, using the colorimetric SOS-chromotest?. Genotoxicity was detected also for Euro0 and Euro1 buses, showing correlation with the ecotoxic potential. The fact that the particulates from Euro4 vehicles did not show ecotoxic/genotoxic effect implies that replacing old Euro1 and Euro2 buses can be a highly effective solution for reducing environmental hazard of automotive emissions. The whole-aerosol testing method is a cheap alternative that can be used in engine developments and emission control.     

Occurrence and behavior of emerging contaminants in surface water and a restored wetland

Pollution mitigation is an important target for restored wetlands, and although there is much information in relation to nutrient removal, little attention has been paid to emerging contaminants. This paper reports on the occurrence and attenuation capacity of 17 emerging contaminants in a restored wetland and two rivers in North-East Denmark. The compounds belong to the groups of pharmaceuticals, fragrances, antiseptics, fire retardants, pesticides, and plasticizers. Concentrations in surface waters ranged from 2 to 1476 ng L⁻¹. The compounds with the highest concentrations were diclofenac, 2-methyl-4-chlorophenoxyacetic acid (MCPA), caffeine, and tris(2-chloroethyl) phosphate (TCEP). The herbicide concentrations increased after a rain-fall event, demonstrating the agricultural run-off origin of these compounds, whereas the concentration of the other emerging contaminants was rather conservative. The mitigation capacity of the restored wetland for the compounds ranged from no attenuation to 84% attenuation (19% on average). Hence, restored wetlands may be considered as a feasible alternative for mitigating emerging contaminants from river waters.     

Comparative acute toxicity of leachates from plastic products made of polypropylene, polyethylene, PVC, acrylonitrile–butadiene–styrene, and epoxy to Daphnia magna

Purpose

The large global production of plastics and their presence everywhere in the society and the environment create a need for assessing chemical hazards and risks associated with plastic products. The aims of this study were to determine and compare the toxicity of leachates from plastic products made of five plastics types and to identify the class of compounds that is causing the toxicity.

Methods

Selected plastic types were those with the largest global annual production, that is, polypropylene, polyethylene, and polyvinyl chloride (PVC), or those composed of hazardous monomers (e.g., PVC, acrylonitrile?Cbutadiene?Cstyrene [ABS], and epoxy). Altogether 26 plastic products were leached in deionized water (3?days at 50°C), and the water phases were tested for acute toxicity to Daphnia magna. Initial Toxicity Identification Evaluations (C18 filtration and EDTA addition) were performed on six leachates.

Results

For eleven leachates (42%) 48-h EC50s (i.e the concentration that causes effect in 50 percent of the test organisms) were below the highest test concentration, 250 g plastic/L. All leachates from plasticized PVC (5/5) and epoxy (5/5) products were toxic (48-h EC50s ranging from 2 to 235?g plastic/L). None of the leachates from polypropylene (5/5), ABS (5/5), and rigid PVC (1/1) products showed toxicity, but one of the five tested HDPE leachates was toxic (48-h EC50 17?C24?g plastic/L). Toxicity Identification Evaluations indicated that mainly hydrophobic organics were causing the toxicity and that metals were the main cause for one leachate (metal release was also confirmed by chemical analysis).

Conclusions

Toxic chemicals leached even during the short-term leaching in water, mainly from plasticized PVC and epoxy products.     

Valorization of pellets from municipal WWTP sludge in lightweight clay ceramics

A direct result of the growing number of municipal wastewater-treatment plants (WWTPs) has been an increase in the generation of large amounts of sewage sludge that requires environmentally acceptable final destination. To decrease the volume of sludge, a common technique is drying the sludge at a low temperature in rotary kilns. The result of this process is a granulated material consisting of dehydrated sludge pellets.After this treatment, this pelletized material becomes easier to manipulate, but it also becomes a more toxic waste, containing dangerous substances, mostly of the lipid type. At its final stage, this material is usually incinerated, used as a comburent material, used as an agricultural fertilizer, or used in the cement industry. Each application has its own problems and requires remediation measures from the safety and environmental viewpoints.In this study, we looked beyond these possible applications and analyzed the transformation of sewage sludge through a ceramization process into a material similar to expanded clays; we subsequently explored its uses in the building industry or in the agriculture industry, among others. Both the properties of the product material and the production method were characterized, and an environmental analysis was conducted.The new, lightweight material had a microstructure with open porosity and low thermal conductivity. Environmental characterization such as the leaching test revealed that undetectable amounts of hazardous metals from the sludge were present in the leachate after the sludge went through a thermal treatment, despite their initial presence (with the exception of vanadium, which could pose some restrictions on some of the proposed uses for the final product). Toxicity tests also showed negative results. The study of gaseous emissions during production revealed emissions factors similar to those during the production of conventional clay ceramics, although with higher organic emissions. As for conventional clay ceramics, industrial production would require the implementation of some type of air-depuration system. The results showed that the ceramization of sludge pellets is a promising valorization technique worth considering from both the economic and technological perspectives.