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.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Functional redundancy and food web functioning in linuron-exposed ecosystems

An extensive data set describing effects of the herbicide linuron on macrophyte-dominated microcosms was analysed with a food web model to assess effects on ecosystem functioning. We showed that sensitive phytoplankton and periphyton groups in the diets of heterotrophs were gradually replaced by more tolerant phytoplankton species as linuron concentrations increased. This diet shift--showing redundancy among phytoplankton species--allowed heterotrophs to maintain their functions in the contaminated microcosms. On an ecosystem level, total gross primary production was up to hundred times lower in the treated microcosms but the uptake of dissolved organic carbon by bacteria and mixotrophs was less sensitive. Food web efficiency was not consistently lower in the treated microcosms. We conclude that linuron predominantly affected the macrophytes but did not alter the overall functioning of the surrounding planktonic food web. Therefore, a risk assessment that protects macrophyte growth also protects the functioning of macrophyte-dominated microcosms.     

Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs)

An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important role in the long-term performance. An integrated study was performed on the Vapokon permeable reactive barrier (PRB) in Denmark by groundwater and iron core sample characterization. The detailed field groundwater sampling carried out from more than 75 well screens up and downstream the barrier showed a very efficient removal (>99%) for the most important CAHs (PCE, TCE and 1,1,1-TCA). However, significant formation of cis-DCE within the PRB resulted in an overall insufficient efficiency for cis-DCE removal. The detailed analysis of the upstream groundwater revealed a very heterogeneous spatial distribution of contaminant loading into the PRB, which resulted in that only about a quarter of the barrier system is treating significant loads of CAHs. Laboratory batch experiments using contaminated groundwater from the site and iron material from the core samples revealed that the aged iron material performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples indicated the presence of a microbial consortium in the barrier. A wide range of species were identified including sulfate and iron reducing bacteria, together with Dehalococcoides and Desulfuromonas species indicating microbial reductive dehalogenation potential. The microbes had a profound effect on the performance of the barrier, as indicated by significant degradation of dichloromethane (which is typically unaffected by zero valent iron) within the barrier.     

Contaminants in the coastal karst aquifer system along the Caribbean coast of the Yucatan Peninsula, Mexico

Intensive land development as a result of the rapidly growing tourism industry in the “Riviera Maya” region of the Yucatan Peninsula, Mexico may result in contamination of groundwater resources that eventually discharge into Caribbean coastal ecosystems. We deployed two types of passive sampling devices into groundwater flowing through cave systems below two communities to evaluate concentrations of contaminants and to indicate the possible sources. Pharmaceuticals and personal care products accumulated in the samplers could only have originated from domestic sewage. PAHs indicated contamination by runoff from highways and other impermeable surfaces and chlorophenoxy herbicides accumulated in samplers deployed near a golf course indicated that pesticide applications to turf are a source of contamination. Prevention and mitigation measures are needed to ensure that expanding development does not impact the marine environment and human health, thus damaging the tourism-based economy of the region.     

Effects of atmospheric ammonia and ammonium sulphate on Douglas fir (Pseudotsuga menziesii)

Three-year-old Douglas firs (Pseudotsuga menziesii) were fumigated with 180 microg m(-3) NH3 or clean (charcoal-filtered) air. During these fumigations the plants received 15 mm artificial rain weekly, supplemented with 20, 500 or 2500 micromol litre(-1) (NH4)2SO4. Exposure to NH3 and NH4+ for 14 weeks resulted in a change of the nutrient status of the needles. The most remarkable effect was the increase in the N/K ratio, due to both uptake of N and leaching of K. The action of NH3 was stronger than that of NH4+. Both NH3 and (NH4)2SO4 affected the epicuticular wax layer and decreased mycorhiza frequency. Following fumigation and artificial rain treatments, needles were incubated for 8 h in a medium containing 0, 50, 250, 500 and 2500 micromol litre(-1) (NH4)2SO4. Almost no exchange of Ca, Mg and K for NH4+ was found. Therefore this ion exchange probably explains only a minor part of the changes in nutrient status of the whole trees.     

Satellite derived trends in NO2 over the major global hotspot regions during the past decade and their inter-comparison

We assessed satellite derived tropospheric NO₂ distribution on a global scale and identified the major NO₂ hotspot regions. Combined GOME and SCIAMACHY measurements for the period 1996-2006 have been used to compute the trends over these regions. Our analysis shows that tropospheric NO₂ column amounts have increased over the newly and rapidly developing regions like China (11 ± 2.6%/year), south Asia (1.76 ± 1.1%/year), Middle East (2.3 ± 1%/year) and South Africa (2.4 ± 2.2%/year). Tropospheric NO₂ column amounts show some decrease over the eastern US (−2 ± 1.5%/year) and Europe (0.9 ± 2.1%/year). We found that although tropospheric NO₂ column amounts decreased over the major developed regions in the past decade, the present tropospheric NO₂ column amounts over these regions are still significantly higher than those observed over newly and rapidly developing regions (except China). Tropospheric NO₂ column amounts show some decrease over South America and Central Africa, which are major biomass burning regions in the Southern Hemisphere.     

Industrial and urban symbiosis in Japan: Analysis of the Eco-Town program 1997–2006

Japan's Eco-Town Program spearheaded in Japan the integration of Industrial Symbiosis and Urban Symbiosis, seeking to maximise the economic and environmental benefit from close geographic proximity of industrial and urban areas, through the use of previously discarded commercial, municipal and industrial waste materials in industrial applications. The program established 26 Eco-Towns around Japan. Approximately 1.65 billion USD was invested in 61 innovative recycling projects, with an average government subsidy of 36%. In addition at least 107 other recycling facilities have been constructed without government subsidy. 14 Eco-Towns primarily contributed to improving industry's productivity, whilst 10 Eco-Towns primarily contributed to improving environmental amenity. In 16 Eco-Towns the private sector was the most important actor supporting local government in the realisation of the Eco-Town, whilst in 9 Eco-Towns this was civil society. The availability of investment subsidies, the coming into force of ambitious recycling legislation with quantified, product-specific targets, access to the significant technological resources of the private sector, and widespread recognition of the urgency to act on environmental issues, all contributed to the success of the Eco-Town Program.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

Contamination of groundwater and risk assessment for arsenic exposure in Ha Nam province, Vietnam

The characteristics of arsenic-contaminated groundwater and the potential risks from the groundwater were investigated. Arsenic contamination in groundwater was found in four villages (Vinh Tru, Bo De, Hoa Hau, Nhan Dao) in Ha Nam province in northern Vietnam. Since the groundwater had been used as one of the main drinking water sources in these regions, groundwater and hair samples were collected in the villages. The concentrations of arsenic in the three villages (Vinh Tru, Bo De, Hoa Hau) significantly exceeded the Vietnamese drinking water standard for arsenic (10 microg/L) with average concentrations of 348, 211, and 325 microg/L, respectively. According to the results of the arsenic speciation testing, the predominant arsenic species in the groundwater existed as arsenite [As(III)]. Elevated concentrations of iron, manganese, and ammonium were also found in the groundwater. Although more than 90% of the arsenic was removed by sand filtration systems used in this region, arsenic concentrations of most treated groundwater were still higher than the drinking water standard. A significant positive correlation was found between the arsenic concentrations in the treated groundwater and in female human hair. The risk assessment for arsenic through drinking water pathways shows both potential chronic and carcinogenic risks to the local community. More than 40% of the people consuming treated groundwater are at chronic risk for arsenic exposure.