Dehalogenases continue to garner interest of the scientific community due to their potential applications in bioremediation of halogen-contaminated environment and in synthesis of various industrially relevant products. Example of such enzymes is DehL, an L-2-haloacid dehalogenase (EC 3.8.1.2) from Rhizobium sp. RC1 that catalyses the specific cleavage of halide ion from L-2-halocarboxylic acids to produce the corresponding D-2-hydroxycarboxylic acids. Recently, the catalytic residues of DehL have been identified and its catalytic mechanism has been fully elucidated. However, the enantiospecificity determinants of the enzyme remain unclear. This information alongside a well-defined catalytic mechanism are required for rational engineering of DehL for substrate enantiospecificity. Therefore, using quantum mechanics/molecular mechanics and molecular mechanics Poisson-Boltzmann surface area calculations, the current study theoretically investigated the molecular basis of DehL enantiospecificity. The study found that R51L mutation cancelled out the dehalogenation activity of DehL towards it natural substrate, L-2-chloropropionate. The M48R mutation, however introduced a new activity towards D-2-chloropropionate, conveying the possibility of inverting the enantiospecificity of DehL from L-to d-enantiomer with a minimum of two simultaneous mutations. The findings presented here will play important role in the rational design of DehL dehalogenase for improving substrate utility.
Satu analisis penentuan parameter kualiti air yang penting untuk penilaian ekosistem cetek telah dilakukan menggunakan kaedah multivariat. Sebanyak 14 parameter kualiti air yang melibatkan komponen biologi, fizik dan kimia telah dikumpulkan setiap bulan selama satu tahun. Data dianalisis menggunakan ujian faktor yang melibatkan tiga proses iaitu mengenal pasti korelasi antara faktor, mengekstrak faktor dan seterusnya melihat kesan gabungan faktor-faktor tersebut. Proses pertama melibatkan pengelompokkan parameter yang berkorelasi kuat ke dalam faktor tersendiri dan mengeluarkan parameter yang mempunyai lebih daripada satu faktor. Analisis pengelasan agglomeratif hierarki (HACA) dan analisis diskriminan (DA) juga dilakukan untuk memperlihatkan kelompokan dan pengaruh faktor terhadap kualiti air tasik. Hasil analisis menunjukkan kualiti air Tasik Chini dipengaruhi oleh lebih daripada satu faktor. Hasil kajian menunjukkan komponen biologi dan kimia (nutrien) mempunyai pengaruh kuat dalam penentuan kualiti air tasik. Parameter berasaskan biologi iaitu BOD5, COD, klorofil a dan kimia (nitrat dan ortofosfat) adalah parameter yang
penting di Tasik Chini. Ketiga-tiga analisis yang dijalankan menunjukkan kepentingan penentuan komponen biologi dan kimia bagi menentukan kualiti air Tasik Chini.
Land application of sludge as fertilizers is a way of disposal and recycling of sludge. However, public concern has arisen due to the fact that organic contaminants in sludge may ultimately enter the food chain. Hence the need arises to analyse the organic contaminants such as PAHs and OCPs in sludge. In this study, Soxhlet was utilised as the extraction method and the extracts subjected to extensive cleanup via either silica columns or solid phase extraction cartridges prior to analysis using gas chromatography or high performance liquid chromatography. Sludge samples were collected from the drying beds of oxidation ponds in three locations in South Johore. OCPs such as heptachlor, dieldrin and pp-DDT were detected in low amounts (52-159 mg/kg) whereas PAHs such as naphthalene, phenanthrene, fluoranthene and benzo(a)pyrene were detected in the range of 0.2-5.5 mg/kg dry mass. Subcritical water extraction (SWE) recovery studies of PAHs were also performed from spiked sludge samples. Although a recovery range of 41-68% was obtained using the SWE method, the results indicated the usefulness of the technique as an alternative to Soxhlet extraction for the analysis of PAHs in sludge samples.
Fenologi tumbuhan menggambarkan fasa kitaran hidup atau aktiviti tumbuhan dan adalah penting untuk memahami
interaksinya dengan iklim. Kajian dilakukan untuk mengenal pasti respons fenologi tumbuhan dan metrik fenologi
hutan dipterokarpa, kelapa sawit dan pokok getah menggunakan data indeks tumbuhan Enhanced Vegetation Index
(EVI) daripada MODIS-Aqua (produk MYD13Q1) dan purata hujan bulanan sepanjang tahun 2007 dan 2009 di negeri
Johor. Pola hujan pada tahun 2007 menunjukkan taburan hujan normal, manakala tahun 2009 mengalami kekurangan
hujan sepanjang tempoh sebelas tahun (2000-2010). Hasil mendapati tren EVI hutan dipterokarpa lebih bervariasi pada
2009 dengan nilai EVI antara 0.39-0.64 berbanding tren pada 2007 yang tekal dengan nilai EVI antara 0.33-0.57. Tren
fenologi kelapa sawit pada 2007 lebih kerap mengalami turun naik berbanding pada 2009, masing-masing dengan EVI
antara 0.45-0.71 dan 0.5-0.74. Corak fenologi pokok getah pada kedua-dua tahun kajian adalah sama dan julat EVI
pada 2009 adalah lebih kecil berbanding 2007, masing-masing dengan EVI antara 0.39-0.62 dan 0.30-0.73. Pengaruh
masa susulan ke atas tahap kehijauan tumbuhan telah dikesan, khususnya selepas peristiwa hujan lebat dalam dua
tahun tersebut dan sedikit sebanyak mempengaruhi nilai korelasi antara pemboleh ubah purata hujan bulanan dengan
EVI tumbuh-tumbuhan. Permulaan dan pengakhiran musim pertumbuhan hutan dipterokarpa bagi kedua-dua tahun
berlaku dalam bulan yang sama, iaitu Februari (permulaan musim) dan Disember (pengakhiran musim). Tidak wujud
perbezaan yang ketara antara panjang musim pertumbuhan kelapa sawit bagi kedua-dua tahun, iaitu hanya 32 hari
lebih panjang pada 2007 berbanding 2009. Musim pertumbuhan pokok getah pula adalah lebih panjang pada 2007 dan
lebih singkat pada 2009, masing-masing 176 hari dan 113 hari.
Members of the catadromous eel live in various fresh, brackish and marine habitats. Therefore, these eels can accumulate organic pollutants and are a suitable bioindicator species for determining the levels of organic contaminants within different water bodies. The ecological risk for organochlorine compounds (OCs) in Anguilla japonica with various migration patterns, such as freshwater, estuarine and marine residences, was examined to understand the specific accumulation patterns. The concentrations of HCB, ∑HCHs, ∑CHLs and ∑DDTs in the silver stage (maturing) eel were significantly higher than those in the yellow stage (immature) eel, in accordance with the higher lipid contents in the former versus the latter. The OC accumulations were clearly different among migratory types in the eel. The ecological risk of OCs increased as the freshwater residence period in the eel lengthened. The migratory histories and the lipid contents directly affected the OC accumulation in the catadromous eel species.
The bioaccumulation of organochlorines (OCs) in the muscle tissue of sea-run (anadromous) and freshwater-resident (fluvial) white-spotted charr (Salvelinus leucomaenis) was determined to assess the ecological risk related to intraspecies variations in diadromous fish life history as they migrate between sea and freshwater. Generally, there were significant correlations between the accumulation of OCs such as DDTs, HCB, HCHs and CHLs. In addition, various biological characteristics, such as total length (TL), body weight (BW) and age, and number of downstream migration (NDM) were correlated. A positive correlation occurred between the lipid content and the OC concentrations. Close linear relationships were found between TL, BW and NDM and the lipid content. Although they are both the same species, the OCs concentrations in the anadromous fish were significantly higher than those in the fluvial individuals. These results suggest that anadromous S. leucomaenis have a higher ecological risk for OCs exposure than the fluvial fish.
Since a few centuries ago, organochlorine compounds (OCs) become one of the threatened contaminants in the world. Due to the lipophilic and hydrophobic properties, OCs always discover in fat or lipid layers through bioaccumulation and biomagnification. The OCs are able to retain in soil, sediment and water for long time as it is volatile, OCs will evaporate from soil and condense in water easily and frequently, which pollute the shelter of aquatic life and it affects the function of organs and damage system in human body. Photocatalysis that employs the usage of semiconductor nanophotocatalyst and solar energy can be the possible alternative for current conventional water remediation technologies. With the benefits of utilizing renewable energy, no production of harmful by-products and easy operation, degradation of organic pollutants in rural water bodies can be established. Besides, nanophotocatalyst that is synthesized with nanotechnology outnumbered conventional catalyst with larger surface area to volume ratio, thus higher photocatalytic activity is observed. In contrast, disadvantages particularly no residual effect in water distribution network, requirement of post-treatment and easily affected by various factors accompanied with photocatalysis method cannot be ignored. These various factors constrained the photocatalytic efficiency via nanocatalysts which causes the full capacity of solar photocatalysis has yet to be put into practice. Therefore, further modifications and research are still required in nanophotocatalysts' synthesis to overcome limitations such as large band gaps and photodecontamination.
Resistance status of Aedes albopictus (Diptera: Culicidae) collected from Sabah, East Malaysia, was evaluated against four major classes of adulticides, namely pyrethroid, carbamate, organochlorine, and organophosphate. Adult bioassays conforming to WHO standard protocols were conducted to assess knockdown and mortality rates of Ae. albopictus. Among tested pyrethroid adulticides, only cyfluthrin, lambda-cyaholthrin, and deltamethrin were able to inflict total knockdown. The other adulticide classes mostly failed to cause any knockdown; the highest knockdown rate was only 18.33% for propoxur. With regards to mortality rate, Ae. albopictus was unanimously susceptible toward all pyrethroids, dieldrin, and malathion, but exhibited resistance toward bendiocarb, propoxur, dichlorodiphenyltrichloroethane, and fenitrothion. Additionally, correlation analysis demonstrated cross-resistance between bendiocarb and propoxur, and malathion and propoxur. In conclusion, this study has disclosed that pyrethroids are still generally effective for Aedes control in Sabah, Malaysia. The susceptibility status of Ae. albopictus against pyrethroids in descending order was cyfluthrin > lambda-cyhalothrin > deltamethrin > etofenprox > permethrin.
The present study aims to investigate the susceptibility status of Aedes albopictus (Skuse) collected from residential areas in Sabah, Malaysia towards eight WHO-recommended dosages of larvicides representing the classes of organophosphates and organochlorines. Field and reference strains of Ae. albopictus larvae were bioassayed in accordance to WHO standard methods using diagnostic dosages of bromophos, malathion, fenthion, fenitrothion, temephos, chlorpyrifos, dichlorodiphenyltrichloroethane (DDT), and dieldrin. The results revealed that Ae. albopictus was resistant (mortality < 90%) towards malathion, temephos, and DDT. In addition, most of the Ae. albopictus strains exhibited a wide range of susceptibilities against bromophos, with mortality ranged from 49.33 to 93.33%. On the contrary, only dieldrin was able to induce 100% mortality against all strains of Ae. albopictus. Tolerance to fenitrothion, fenthion, and chlorpyrifos, with mortality ranging from 81.33 to 97.33%, was also observed in this study.
Occurrence and distribution of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), and pyrethroid pesticides (PYRs) residues in the leafy vegetables were analyzed together with the soil samples using gas chromatography-electron capture detector. Edible tissues of vegetables showed detectable residues of these compounds indicating the influence of the conventional farms and nearby organic farms. In the vegetables, the OCPs concentrations were recorded as nd-133.3 ng/g, OPPs as nd-200 ng/g, and PYRs as nd-33.3 ng/g. In the soil, the OCPs concentrations were recorded as nd-30.6 ng/g, OPPs as nd-26.6 ng/g, and for PYRs as nd-6.7 ng/g. Bioconcentration factor (BCF) was higher for the OPPs (0.3) than the OCPs and PYRs (1.1). The OCPs concentration in the vegetables decreased in the following order: spinach > celery > broccoli > cauliflower > cabbage > lettuce > mustard. For OPPs, the concentration decreased in the following order: cauliflower > spinach > celery > cabbage > broccoli > lettuce > mustard and for PYRs as spinach > celery > lettuce > cabbage > broccoli. Principal component analysis indicates that the sources of these pesticides are not the same, and the pesticide application on the vegetables depends on the type of crop. There is a significant positive correlation between OPPs and the soil (r = 0.65) as compared to OCPs and PYRs (r = 0.1) as the vegetables accumulated OPPs more efficiently than OCPs and PYRs.
Kajian kuasai-eksperimental ini dijalankan bertujuan untuk mengukur kesan terapi keluarga ke atas herotan kognitif pesalah remaja. Subjek kajian terdiri daripada 18 orang pesalah jenayah remaja yang menerima perintah bon berkelakuan baik berserta perintah tambahan bengkel interaktif sebagai kumpulan rawatan dan 18 orang pesalah remaja yang menerima perintah bon berkelakuan baik tanpa perintah tambahan bengkel interaktif sebagai kumpulan kawalan. Herotan kognitif diukur menggunakan soal selidik laporan kendiri Cognitive Distortion Scale (CDS). Subjek rawatan diberikan enam sesi terapi keluarga dalam jangka masa 2 - 3 bulan selama 50 ke 90 minit bagi setiap sesi. Ujian SPANOVA digunakan untuk mengukur kesan terapi keluarga ke atas pesalah remaja. Hasil kajian menunjukkan terapi keluarga berkesan secara signifikan untuk mengurangkan herotan kognitif pesalah remaja.
This study describes the development of a multimedia environmental fate and transport model of dichlorodiphenyltrichloroethane (DDT) at Sungai Sayong watershed. Based on the latest estimated DDT emission, the DDT concentrations in air, soil, water and sediment as well as the transfer processes were simulated under the equilibrium and steady-state assumption. Model predictions suggested that soil and sediment was the dominant sink of DDT. The results showed that the model predicted was generally good agreement with field data. Compared with degradation reaction, advection outflow was more important processes occurred in the model. Sensitivities of the model estimates to input parameters were tested. The result showed that vapour pressure (Ps) and organic carbon water partition coefficient (KOC) were the most influential parameters for the model output. The model output-concentrations of DDT in multimedia environment is very important as it can be used in future for human exposure and risk assessment of organochlorine pesticides (OCPs) at Sungai Sayong Basin.
The non-stereospecific α-haloalkanoic acid dehalogenase DehE from Rhizobium sp. RC1 catalyzes the removal of the halide from α-haloalkanoic acid D,L-stereoisomers and, by doing so, converts them into hydroxyalkanoic acid L,D-stereoisomers, respectively. DehE has been extensively studied to determine its potential to act as a bioremediation agent, but its structure/function relationship has not been characterized. For this study, we explored the functional relevance of several putative active-site amino acids by site-specific mutagenesis. Ten active-site residues were mutated individually, and the dehalogenase activity of each of the 10 resulting mutants in soluble cell lysates against D- and L-2-chloropropionic acid was assessed. Interestingly, the mutants W34→A,F37→A, and S188→A had diminished activity, suggesting that these residues are functionally relevant. Notably, the D189→N mutant had no activity, which strongly implies that it is a catalytically important residue. Given our data, we propose a dehalogenation mechanism for DehE, which is the same as that suggested for other non-stereospecific α-haloalkanoic acid dehalogenases. To the best of our knowledge, this is the first report detailing a functional aspect for DehE, and our results could help pave the way for the bioengineering of haloalkanoic acid dehalogenases with improved catalytic properties.
Nineteen pairs of gaseous and surface seawater samples were collected along the cruise from Malaysia to the south of Bay of Bengal passing by Sri Lanka between April 12 and May 4, 2011 on the Chinese research vessel Shiyan I to investigate the latest OCP pollution status over the equatorial Indian Ocean. Significant decrease of α-HCH and γ-HCH was found in the air and dissolved water phase owing to global restriction for decades. Substantially high levels of p,p'-DDT, o,p'-DDT, trans-chlordane (TC), and cis-chlordane (CC) were observed in the water samples collected near Sri Lanka, indicating fresh continental riverine input of these compounds. Fugacity fractions suggest equilibrium of α-HCH at most sampling sites, while net volatilization for DDT isomers, TC and CC in most cases. Enantiomer fractions (EFs) of α-HCH and o,p'-DDT in the air and water samples were determined to trace the source of these compounds in the air. Racemic or close to racemic composition was found for atmospheric α-HCH and o,p'-DDT, while significant depletion of (+) enantiomer was found in the water phase, especially for o,p'-DDT (EFs = 0.310 ± 0.178). 24% of α-HCH in the lower air over the open sea of the equatorial Indian Ocean is estimated to be volatilized from local seawater, indicating that long-range transport is the main source.
The use of organochlorine pesticides has caused concern due to their effects on human health and the Malaysian aquatic ecosystem, particularly so in view of their persistent and bioaccumulative properties. Since the extent of organochlorine pesticide pollution in Malaysian waterways is unknown except for isolated instances, a systematic survey has now been carried out. Water samples from various rivers were extracted, cleaned up with Florisil and analysed for the individual organochlorine pesticides by gas chromatography (GC) with an electron capture detector (ECD). DDE, DDT and heptachlor were present in all the river water samples of the west coast of Peninsular Malaysia. Other organochlorine pesticides were also identified from the water samples. However, the levels of all these are still below criteria values for Malaysian aquatic life, indicating that organochlorine pesticide pollution is less of a problem than other organic or inorganic pollutants.
In this study on green turtles, Chelonia mydas, from Peninsular Malaysia, the effect of selected environmental toxicants was examined in vitro. Emphasis was placed on purported hormone-mimicking chemicals such as dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethylene, dieldrin, lead, zinc and copper. Five concentrations were used: high (1 mg/L), medium (10(-1) mg/L), low (10(-2) mg/L), very low (10(-6) mg/L) and control (diluted carrier solvent but no toxicants). The results suggest that environmental pesticides and heavy metals may significantly alter the binding of steroids [i.e. testosterone (T) and oestradiol] to the plasma proteins in vitro. Competition studies showed that only Cu competed for binding sites with testosterone in the plasma collected from nesting C. mydas. Dieldrin and all heavy metals competed with oestradiol for binding sites. Furthermore, testosterone binding affinity was affected at various DDT concentrations and was hypothesised that DDT in vivo may act to inhibit steroid-protein interactions in nesting C. mydas. Although the precise molecular mechanism is yet to be described, DDT could have an effect upon the protein conformation thus affecting T binding (e.g. the T binding site on the steroid hormone binding protein molecule).
A new cobalt(II) ion selective electrode based on palladium(II) dichloro acetylthiophene fenchone azine(I) has been developed. The best membrane composition is found to be 10:60:10:21.1 (I)/PVC/NaTPB/DOP (w/w). The electrode exhibits a Nerstian response in the range of 1.0 × 10(-1)-1.0 × 10(-6)M with a detection limit and slope of 8.0 × 10(-7)M and 29.6 ± 0.2 mV per decade respectively. The response time is within the range of 20-25s and can be used for a period of up to 4 months. The electrode developed reveals good selectivity for cobalt(II) and could be used in pH range of 3-7. The electrode has been successfully used in the determination of cobalt(II) in water samples.
Persistent organochlorines in air, river water and sediment samples were analysed from eastern and southern Asia (India, Thailand, Vietnam, Malaysia, Indonesia) and Oceania (Papua New Guinea and Solomon Islands) to elucidate their geographical distribution in tropical environment. The concentrations of organochlorines in these abiotic samples collected from Taiwan, Japan and Australia were also monitored for comparison. Atmospheric and hydrospheric concentrations of HCHs (hexachlorocyclohexanes) and DDTs (DDT and its metabolites) in the tropical developing countries were apparently higher than those observed in the developed nations, suggesting extensive usage of these chemicals in the lower latitudes. CHLs (chlordane compounds) and PCBs (polychlorinated biphenyls) were also occasionally observed at higher levels in the tropics, implying that their usage area is also expanding southward. Distribution patterns of organochlorines in sediments showed smaller spatial variations on global terms, indicating that the chemicals released in the tropical environment are dispersed rapidly through air and water and retained less in sediments. The ratios of organochlorine concentrations in sediment and water phases were positively correlated with the latitude of sampling, suggesting that persistent and semivolatile compounds discharged in the tropics tend to be redistributed on a global scale.
A headspace single-drop microextraction (HS-SDME) procedure is optimized for the analysis of organochlorine and organophosphorous pesticide residues in food matrices, namely cucumbers and strawberries by gas chromatography with an electron capture detector. The parameters affecting the HS-SDME performance, such as selection of the extraction solvent, solvent drop volume, extraction time, temperature, stirring rate, and ionic strength, were studied and optimized. Extraction was achieved by exposing 1.5 microL toluene drop to the headspace of a 5 mL aqueous solution in a 15-mL vial and stirred at 800 rpm. The analytical parameters, such as linearity, correlation coefficients, precision, limits of detection (LOD), limits of quantification (LOQ), and recovery, were compared with those obtained from headspace solid-phase microextraction (HS-SPME) and solid-phase extraction. The mean recoveries for all three methods were all above 70% and below 104%. HS-SPME was the best method with the lowest LOD and LOQ values. Overall, the proposed HS-SDME method is acceptable in the analysis of pesticide residues in food matrices.