Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

Anaerobic degradation behavior of nonylphenol polyethoxylates in sludge

Anaerobic biodegradation behavior of nonylphenol polyethoxylates (NPEOs) was investigated. Results showed that terminal electron acceptors, organic matters, initial concentration, and temperature had great influence on the anaerobic biodegradation of NPEOs. Anaerobic biodegradation of NPEOs could be enhanced by adding sulfate or nitrate while this process could be inhibited by adding organic matters. The maximum removal rate increased 1.24 microM d(-1) for each ten micromoles increase in initial concentration. The decrease in temperature caused a sharp decrease in the removal efficiency of NPEOs. The temperature coefficient (PHI) for the anaerobic biodegradation of NPEOs was 0.01 degrees C(-1). Nonylphenol (NP), the typical intermediate of NPEOs, could inhibit the anaerobic biodegradation of NPEOs only at high concentration. However, these environmental factors had no effect on the anaerobic biodegradation pathway of NPEOs. The accumulation of NP and short-chain NPEOs during NPEO biodegradation led to a significant increase in the estrogenic activity during the biodegradation period.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

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.     

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.     

Oxidation of elemental mercury using atmospheric pressure non-thermal plasma

The oxidation of gas phase elemental mercury (Hg0) by atmospheric pressure non-thermal plasma has been investigated at room temperature, employing both dielectric barrier discharge (DBD) of the gas mixture of Hg0 and injection of ozone (O3) into the gas mixture of Hg0. Results have shown that the oxidative efficiencies of Hg0 by DBD and the injection of O3 are 59% and 93%, respectively, with energy consumption of 23.7 J L(-1). This combined approach has indicated that O3 plays a decisive role in the oxidation of gas phase Hg0. Also the oxidation of Hg0 by injecting O3 into the gas mixture of Hg0 proceeds with better efficiency than DBD of the gas mixture of Hg0. These results have been explained by the incorporation of the competitive reaction pathways between the formation of HgO by O3 and the decomposition of HgO back to Hg0 in the plasma environment.     

Synthesis and analytical follow-up of the mineralization of a new fluorosurfactant prototype

Fluorinated surfactants have become essential in numerous technical applications due to their unparalleled effectiveness and efficiency. The environmental persistence of the non-biodegradable perfluorinated alkyl moiety has become a matter of concern. Therefore, it was searched for new molecules with chemically stable fluorinated end groups which can be microbially transformed into labile fluorinated substances. One prototype substance, 10-(trifluoromethoxy)decane-1-sulfonate, has shown biomineralization. Monitoring the formation of metabolites over time elucidated the mechanism of biotransformation. Analysis was performed utilizing liquid chromatography-single quadrupole mass spectrometry (LC-MS) and quadrupole-time of flight tandem mass spectrometry (QqTOF-MS). It was possible to distinguish between two major degradation pathways of the fluorinated alkylsulfonate derivative: (i) a desulfonation and subsequent oxidation and degradation of the alkyl chain being predominant and (ii) an insertion of oxygen with a subsequent cleavage and degradation of the molecule. The utilized trifluoromethoxy-endgroup resulted in instable trifluoromethanol after degradation of the alkyl chain, which led to a high degree of mineralization of the molecule.     

Cadmium stress alters gene expression of DNA mismatch repair related genes in Arabidopsis seedlings

Cadmium (Cd) is a non essential element, and is a widespread environmental pollutant. Exposure to Cd can result in a variety of adverse health effects in plant and humans. In the current study, Arabidopsis seedlings were used as a bio-indicator of Cd pollution. Seedlings were grown on MS media containing 0-6.0 mg L(-1) Cd for 18 days, and the gene expression patterns were used to link increased Cd exposure with progressive biological effects. Reduction of total soluble protein content in shoots of the Arabidopsis seedlings occurred with increase in Cd concentrations. For the gene expression patterns, seven genes known to be involved in cell division and DNA mismatch repair (MMR) system were investigated by semi-quantitative RT-PCR, and normalized using 18S rRNA gene expression. Expression of the proliferating cell nuclear antigen 2 (atPCNA 2), MutS 3 homolog (atMSH 3) and MutL1 homolog (atMLH1) genes in shoots of Arabidopsis was strongly induced by exposure to 0.75 mg L(-1) Cd, but were repressed by other Cd concentrations whereas exposure to 0.75-6 mg L(-1) of Cd resulted in a decreased expression of atPCNA1, atMSH 2, 6 and 7 genes independently of any observable biological effects, including survival, fresh weight and chlorophyll level of shoots. This work demonstrated that specific gene expression changes could serve as useful molecular biomarkers indicative of Cd exposure and related biological effects.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.