National Committee on Marine Sciences (NCMS)
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- In Silico supported nontarget analysis of contaminants of emerging concern: Increasing confidence in unknown identification in wastewater and surface watersAngeles, Luisa F.; Halwatura, Lahiruni M.; Antle, Jonathan P.; Simpson, Scott; Jaraula, Caroline M.B.; Aga, Diana S. (American Chemical Society, 2021-08-01)Nontarget analysis using liquid chromatography–high resolution mass spectrometry (LC–HRMS) is a valuable approach in characterizing for contaminants of emerging concern (CECs) in the environment. In this study, wastewater and surface water samples from three locations in Manila, Philippines were analyzed for CECs using a nontarget analysis approach with an LC-Orbitrap. A previously optimized semiautomated workflow was used for data processing with Compound Discoverer. A total of 157 compounds were identified, with 21 confirmed with reference standards, 83 confirmed with evidence from a mass spectral library (mzCloud), and 53 tentatively identified using in silico fragmentation (MetFrag). These compounds include pharmaceuticals such as antibiotics, antifungal, and antihypertensive compounds, human metabolites, natural products, pesticides, and industrial chemicals. Compounds confirmed with reference standards include antibiotics ciprofloxacin, clarithromycin, acetyl-sulfamethoxazole, and trimethoprim (2 to 19 ng/L), and antifungal compounds carbendazim and climbazole (3–47 ng/L). The pesticides diethyltoluamide (DEET) and diuron were also detected (37 ng/L). The utility of a preliminary multivariable linear regression quality structure-retention relationship (QSRR) model based on quantum chemical molecular descriptors is demonstrated. This study demonstrates the importance of using tools and software that are helpful for annotating HRMS data and reporting detections according to a standardized classification system. The detection of several CECs in wastewater and surface water samples show the importance of performing nontarget analysis in determining occurrence of CECs in the environment.We acknowledge support from the National Science Foundation PIRE-HEARD award number 1545756 and USAID PEER subaward number 2000009924. S.S. thanks the National Science Foundation (Award #1904825) for support of this research, and the Donors of the American Chemical Society Petroleum Research Fund (PRF-58954-UNI5). We also thank Shyrill Mae Mariano from the Marine Science Institute in the University of the Philippines − Diliman who helped with the sample collection and Rebecca Dickman from University at Buffalo for her help on technical work.
- Utility of low-cost recreational-grade echosounders in imaging and characterizing bubbly coastal submarine groundwater dischargeGabuyo, Mary Rose P.; Siringan, Fernando P. (Elsevier, 2022-01)Despite the growing knowledge on the significance of submarine groundwater discharge (SGD), mapping its occurrence is a continuing challenge. This study explores the capability and applicability of low-cost, off-the-shelf, recreational-grade echosounders (RGESs) to image different types and locate point sources of bubbly coastal SGD. Standard and systematic methodologies for efficient imaging and processing were established. The use of RGES was validated using a research-grade side scan sonar (RGSSS), continuous resistivity profiling, conductivity-temperature-depth casting, and MantaCam and SCUBA diving surveys. Lower frequencies (77/83 kHz) of RGESs showed more distinct acoustic signatures of bubbly SGD, as these were nearly the same as the effective resonance frequency of the bubbles. The clusters of bubbly discharges have higher backscatter strength than the water column noise, resulting in the definitive and convenient manual detection of SGD features. Hence, showing more accurate point sources of SGD. Three types of known SGD occurrence were identified and characterized based on acoustic behavior and spatial distribution: 1) sparse, discrete and sporadic discharge over wide area, 2) curtain, high and continuous bubble concentrations from widespread discharge, and 3) spring, direct bubble discharge from intense seafloor degassing at a single point source. These results showed that RGES provides a good alternative for more efficient and cost-effective preliminary coastal SGD works. Additional research on areas with water-dominated discharge but no bubbling is recommended.
- Clay mineral nanostructures regulate sequestration of organic carbon in typical fluvial sedimentsSong, Hongzhe; Liu, Zhifei; Lin, Baozhi; Zhao, Yulong; Siringan, Fernando P.; You, Chen-Feng (Elsevier, 2024-02-15)The association between clay minerals and organic carbon is pivotal for understanding transport, burial, and preservation processes of sedimentary organic carbon. However, fine-scale microscopic studies are still limited in assessing the effect of diverse clay mineral structures and properties on organic carbon sequestration. In this study, we employed X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy coupled with energy dispersive spectroscopy and electron energy loss spectroscopy analyses to investigate the nanoscale interaction between clay minerals and organic carbon of two typical fluvial sediment samples with contrasting clay mineral compositions and organic carbon origins. Sample from Taiwan shows abundant illite and chlorite with petrogenic organic carbon, while sample from Luzon has significant smectite with pedogenic organic carbon. We observed that the nanostructure of the clay minerals controls the distribution of organic carbon. In the Luzon sample, the organic carbon is tightly associated with smectite, occupying expandable interlayer spaces. In the Taiwan sample, however, the organic carbon is primarily confined on the surface and edge of illite. These findings offer valuable insights into the selective association of organic carbon with clay minerals and underscore the role of clay mineral nanolayer structures in governing the occurrence and preservation of organic carbon in sediments. A comprehensive understanding of these interactions is crucial for accurate assessments of carbon cycling and sequestration in the natural environment.We sincerely thank Shunai Che and Lu Han for their help in TEM experiments and data processing. We thank Editor Dr. Andrew Hursthouse for handling the manuscript and two anonymous reviewers for their constructive comments on the early version of this paper. This work was supported by the National Natural Science Foundation of China (42130407, 42188102, 42306066) and the Interdisciplinary Project of Tongji University (ZD-22-202102).
- Emerging pharmaceutical contaminants in key aquatic environments of the PhilippinesMariano, Shyrill Mae F.; Angeles, Luisa F.; Aga, Diana S.; Villanoy, Cesar L.; Jaraula, Caroline Marie B. (Frontiers Media SA, 2023-09-13)Pharmaceuticals in natural waters are considered emerging pollutants due to their low concentrations and the negative effects they pose to the environment. Common sources of such pollutants include untreated wastewater from hospitals, residential, industrial, and agricultural sources. Many wastewater treatment methods only remove a subset of all pharmaceuticals from the wastewater; remaining pharmaceuticals are discharged into natural waters, and ultimately drain into coastal areas. Regions without proper wastewater treatment are especially susceptible to such contamination. This study deals with the distribution, sources, and seasonal variability of pharmaceuticals in key aquatic systems in the Philippines. Two watershed continuums (Davao Gulf, Davao City; Macajalar Bay, Cagayan de Oro City); two tourist areas (Boracay Island, Aklan; Mabini, Batangas); and one pristine atoll (Tubbataha Reefs, Palawan)—all with varied prevailing human population pressures—were studied. Samples of hospital wastewater as well as groundwater, surface and bottom water samples from rivers and coastal seas collected during dry and wet seasons were analyzed using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Thirty-four target pharmaceutical residues and antibiotics were extracted and quantified. Acetaminophen was detected at concentrations of up to 289.17 ppb in freshwater samples, and at concentrations of up to 253.39 ppb in seawater samples. Ubiquitous to all the sites was caffeine, reaching 1848.57 ppb. Sulfamethazine, a commonly used veterinary antibiotic, was detected at 764.91 ppb in a river site in Cagayan de Oro. Untreated hospital wastewater contained metformin, iopamidol, sulfamethoxazole, acetylsulfamethoxazole, ciprofloxacin, and azithromycin, but these pharmaceuticals were not detected in other river and coastal waters. Samples collected during the dry season exhibited higher concentrations than those from the wet season, which appears to be related to increase in transient populations from tourism activities as well as dilution. The presence of pharmaceutical residues and antibiotics in these areas and the potential impact on the environment indicate the need for stricter wastewater management measures, particularly in communities located near water bodies. As the results of this study show, such measures might be most beneficial and effective if imposed during dry season and in areas open to tourism.We thank the crew and researchers aboard M/Y Panata expedition PA0421 to Tubbataha in October 2019 and cruise to Boracay December 2019. Our gratitude to Mary Antoinette Limen, Mishel Valery Rañada, Gio Ferson Bautista, and Ernest Guiller Pineda for helping us in the field, and to Lahiruni Halwatura for assisting in the creation of a standard calibration curve for saltwater.
- BFAR Administrative Circular No. 256: Series of 2015. Declaring malachite green and gentian violet as health hazards and prohibiting their use in food fish production and trade.(Bureau of Fisheries and Aquatic Resources, 2015-02-12)This Circular, consisting of 25 Sections divided into seven Chapters and one Annex, prohibits the use of malachite green and gentian violet in all stages of aquaculture production of fishery and aquatic products intended for human consumption and the distribution for commerce of fishery and aquatic products derived from aquaculture containing traces of the dyes. It shall be unlawful for any person to: 1) Use malachite green or gentian violet in the aquaculture production of food fish; 2) Produce, handle or process for sale, offer for sale, distribute in commerce fish or fishery product bearing or containing malachite green or gentian violet; and, 3) Import into the Philippines or export fish or fishery product bearing or containing malachite green or gentian violet. Any importer, exporter, aquaculture/farm operator, or distributor found violating any of the provisions of this Circular shall be subject to the following administrative sanctions: a) for the first offense, suspension for three months of the registration as importer, exporter, aquaculture/farm operator or distributor; b) for the second offense, six-month suspension of the registration; and, c) for the third offense, revocation of the registration and delisting.