Review on the use of enzymes for the detection of organochlorine, organophosphate and carbamate pesticides in the environment

Pesticides are released intentionally into the environment and, through various processes, contaminate the environment. Three of the main classes of pesticides that pose a serious problem are organochlorines, organophosphates and carbamates. While pesticides are associated with many health effects, there is a lack of monitoring data on these contaminants. Traditional chromatographic methods are effective for the analysis of pesticides in the environment, but have limitations and prevent adequate monitoring. Enzymatic methods have been promoted for many years as an alternative method of detection of these pesticides. The main enzymes that have been utilised in this regard have been acetylcholinesterase, butyrylcholinesterase, alkaline phosphatase, organophosphorus hydrolase and tyrosinase. The enzymatic methods are based on the activation or inhibition of the enzyme by a pesticide which is proportional to the concentration of the pesticide. Research on enzymatic methods of detection, as well as some of the problems and challenges associated with these methods, is extensively discussed in this review. These methods can serve as a tool for screening large samples which can be followed up with the more traditional chromatographic methods of analysis.     

Industrial wastewater pre-treatment for heavy metal reduction by employing a sorbent-assisted ultrafiltration system

This work examined the adoption of a sorbent-assisted ultrafiltration (UF) system for the reduction of Pb(II), Cu(II), Zn(II) and Ni(II) from industrial wastewater. In such a system metals were removed via several processes which included precipitation through the formation of hydroxides, formation of precipitates/complexes among the metal ions and the wastewater compounds, adsorption of metals onto minerals (bentonite, zeolite, vermiculite) and retention of insoluble metal species by the UF membranes. At pH = 6 the metal removal sequence obtained by the UF system was Pb(II) > Cu(II) > Zn(II) > Ni(II) in mg g⁻¹ with significant amount of lead and copper being removed due to chemical precipitation and formation of precipitates/complexes with wastewater compounds. At this pH, zinc and nickel adsorption onto minerals was significant, particularly when bentonite and vermiculite were employed as adsorbents. Metal adsorption onto zeolite and bentonite followed the sequence Zn(II) > Ni(II) > Cu(II) > Pb(II), while for vermiculite the sequence was Ni(II) > Zn(II) > Cu(II) > Pb(II) in mg g⁻¹. The low amount of Pb(II) and Cu(II) adsorbed by minerals was attributed to the low available lead and copper concentration. At pH = 9 the adoption of UF could effectively reduce heavy metals to very low levels. The same was observed at pH = 8, provided that minerals were added. The prevailing metal removal process was the formation of precipitates/complexes with wastewater compounds.     

Temporal and geographical genetic variation in the amphipod Melita plumulosa (Crustacea: Melitidae): Link of a localized change in haplotype frequencies to a chemical spill

Anthropogenic effects such as contamination affect the genetic structure of populations. This study examined the temporal and geographical patterns of genetic diversity among populations of the benthic crustacean amphipod Melita plumulosa in the Parramatta River (Sydney, Australia), following an industrial chemical spill. The spill of an acrylate/methacrylate co-polymer in naphtha solvent occurred in July 2006. M. plumulosa were sampled temporally between December 2006 and November 2009 and spatially in November 2009. Genetic variation was examined at the mitochondrial cytochrome c oxidase subunit I locus. Notably, nucleotide diversity was low and Tajima’s D was significantly negative amongst amphipods collected immediately downstream from the spill for 10 months. We hypothesize that the spill had a significant localized effect on the genetic diversity of M. plumulosa. Alternate explanations include an alternate and unknown toxicant or a localized sampling bias. Future proposed studies will dissect these alternatives.     

Enhanced retention of linuron, alachlor and metalaxyl in sandy soil columns intercalated with wood barriers

A study has been made of the effect a reactive barrier made of pine (softwood) or oak (hardwood) wood intercalated in a sandy soil column has on the retention of linuron, alachlor and metalaxyl (pesticides with contrasting physicochemical characteristics). The leaching of pesticides has been carried out under a saturated flow regime and breakthrough curves (BTCs) have been obtained at flow rates of 1 mL min⁻¹ (all pesticides) and 3 mL min⁻¹ (linuron). The cumulative curves in the unmodified soil indicate a leaching of pesticides >80% of the total amount of compound added. After barrier intercalation, linuron leaching decreases significantly and a modification of the leaching kinetics of alachlor and metalaxyl has been observed. The theoretical R factors increased ∼2.6-3.3, 1.2-1.6-fold, and 1.4-1.7-fold and the concentration of the maximum peak decreased ∼6-12-fold, 2-4-fold and 1.2-2-fold for linuron, alachlor and metalaxyl, respectively. When considering the three pesticides, significant correlations have been found between the theoretical retardation factor (R) and the pore volume corresponding to the maximum peaks of the BTCs (r = 0.77; p < 0.05) or the total volume leached (r = −0.78; p < 0.05). The results reveal the efficacy of reactive wood barriers to decrease the leaching of pesticides from point sources of pollution depends on the type of wood, the hydrophobicity of the pesticide and the adopted water flow rate. Pine was more effective than oak in decreasing the leaching of hydrophobic pesticide linuron or in decreasing the maximum peak concentration of the less hydrophobic pesticides in soils. Efficacy of these wood barriers was limited for the least hydrophobic pesticide metalaxyl.     

Terrestrial exposure of oilfield flowline additives diminish soil structural stability and remediative microbial function

Onshore oil production pipelines are major installations in the petroleum industry, stretching many thousands of kilometres worldwide which also contain flowline additives. The current study focuses on the effect of the flowline additives on soil physico-chemical and biological properties and quantified the impact using resilience and resistance indices. Our findings are the first to highlight deleterious effect of flowline additives by altering some fundamental soil properties, including a complete loss of structural integrity of the impacted soil and a reduced capacity to degrade hydrocarbons mainly due to: (i) phosphonate salts (in scale inhibitor) prevented accumulation of scale in pipelines but also disrupted soil physical structure; (ii) glutaraldehyde (in biocides) which repressed microbial activity in the pipeline and reduced hydrocarbon degradation in soil upon environmental exposure; (iii) the combinatory effects of these two chemicals synergistically caused severe soil structural collapse and disruption of microbial degradation of petroleum hydrocarbons.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.     

Substituting missing data in compositional analysis

Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study.     

Mobile passive samplers: concept for a novel mode of exposure

Integrative passive sampling with devices such as semipermeable membrane devices generally relies on rigs for month-long static exposures in water. We evaluate here whether mobile exposures of passive samplers can provide reliable estimates of dissolved contaminant concentrations. Mobile exposures were obtained by towing samplers fastened to the end of a benthic trawl net. Significant and reproducible absorption of polycyclic aromatic hydrocarbons during 5 h-long deployments was made possible by high sampling rates resulting from high water turbulences during towing at 1.2-1.5 knots. Sampling rates (72-215 L d⁻¹) estimated from the dissipation of performance reference compounds were supported by in situ calibration with samplers exposed for a 30 days in the vicinity of the test site. Higher fluoranthene and pyrene absorption in samplers exposed to the trawling-induced sediment plume could be attributed to desorption from re-suspended sediments. This mode of exposure has the potential to be used in monitoring programmes.     

Ecological impacts of the N-viro biosolids land-application for wild blueberry (Vaccinium angustifolium. Ait) production in Nova Scotia

Land application of biosolids from processed sewage sludge may deteriorate soil, water, and plants. We investigated the impact of the N-Viro biosolids land-application on the quality of the soil water that moved through Orthic Humo-Ferric Podzols soil of Nova Scotia (NS) at the Wild Blueberry Research Institute, Debert, NS Canada. In addition, the response of major soilproperties and crop yield was also studied. Wild blueberry (Vaccinium angustifolium. Ait) was grown under irrigated and rainfed conditions in 2008 and 2009. Four experimental treatments including (i) NI: N-Viro irrigated, (ii) NR: N-Viro rainfed, (iii) FI: inorganic fertilizer irrigated, and (iv) FR: inorganic fertilizer rainfed (control) were replicated 4 times under randomized complete block design. Soil samples were collected at the end of each year and analyzed for changes in cation exchange capacity (CEC), soil organic matter (SOM), and pH.Soil water samples were collected four times during the study period from the suction cup lysimeters installed within and below crop root zone at 20 and 40 cm depths, respectively. The samples were analyzed for a range of water quality parameters including conductance, hardness, pH, macro- and micronutrients, and the infectious pathogens Escherichia coli (E. coli) and salmonella. Berries were harvested for fruit yield estimates. Irrigation significantly increased CEC during 2008 and the soil pH decreased from 4.93 (2008) to 4.79 (2009). There were significant influences of irrigation, fertilizer, and their interaction, in some cases, on most of the soil water quality parameters except on the infectious bacteria. No presence of E. coli or salmonella were observed in soil and water samples, reflecting the absence of these bacteria in biosolids used in this experiment. Nutrient concentration in the soil water samples collected from the four treatments were higher in the sequence NI > NR > FI > FR. The irrigation treatment had significant effect on the unripe fruit yield. We conclude that the comparable performance of N-Viro biosolids and the increasing prices of inorganic fertilizers would compel farmers to use economically available N-Viro biosolids that, coupled with the supplemental irrigation, did not deteriorate the studied soil properties, soil water quality, and the wild blueberry yield during this experiment.     

Mineralization and degradation of glyphosate and atrazine applied in combination in a Brazilian Oxisol

The aim of this study was to investigate the behavior of the association between atrazine and glyphosate in the soil through mineralization and degradation tests. Soil treatments consisted of the combination of a field dose of glyphosate (2.88 kg ha?1) with 0, ?, 1 and 2 times a field dose of atrazine (3.00 kg ha?1) and a field dose of atrazine with 0, ?, 1 and 2 times a field dose of glyphosate. The herbicide mineralization rates were measured after 0, 3, 7, 14, 21, 28, 35, 42, 49, 56 and 63 days of soil application, and degradation rates after 0, 7, 28 and 63 days. Although glyphosate mineralization rate was higher in the presence of 1 (one) dose of atrazine when compared with glyphosate alone, no significant differences were found when half or twice the atrazine dose was applied, meaning that differences in glyphosate mineralization rates cannot be attributed to the presence of atrazine. On the other hand, the influence of glyphosate on atrazine mineralization was evident, since increasing doses of glyphosate increased the atrazine mineralization rate and the lowest dose of glyphosate accelerated atrazine degradation.