Annual Report for 2001-2002

UNU Project on EDC Monitoring in the East Asian Hydrosphere

Participating Country: Philippines

Submitted by Dr. Evangeline C. Santiago

National Project Coordinator

1. Introduction.

The participation of the Philippines in the UNU project on Monitoring of EDCs in the East Asian Coastal Hydrosphere continues to be a strong force in the capability building of the Natural Sciences Research Institute to monitor organic pollutants in the Philippine environment. At present, the Philippines does not have a single laboratory capable of doing analysis of trace organic pollutants. The analytical methods and the equipment provided by Shimadzu for the project greatly speeded -up our laboratory's program to develop such capability at the Natural Sciences Research Institute. The inclusion of the phthalate analysis in the monitoring activity for the third year gave us the opportunity to learn a new analysis. The continuation of the monitoring of the OCPs and phenols gave us the necessary drive to refine the performance of the methods in our laboratory.

2. Sampling Procedures

2.1 Selection of Locations

The sampling sites that were selected in the second year of the project on the basis of proximity to industrial sources were retained for the third year monitoring activities. The previous sampling scheme was adopted to provide continuity of the monitoring of the OCPs and phenols. Since the sites are close to industrial activities, the study areas would also be suitable for monitoring of phthalates. The sampling sites include 10 river sites and 9 coastal sites in the cities of Manila, Batangas and Subic and the town of Limay in Bataan. The exact locations of the sampling sites and the corresponding laboratory codes for each site are listed in Table 1.

2.2 Samples Collected

Surface water and bottom water samples were collected for the required UNU parameters, OCPs, phenols and phthalates and additional parameter PCBs which is not required by the project. Table 2. lists the sample codes used for the analysis.

Sediment samples were also collected for OCPs and PCBs analysis.

Surface water and bottom water and sediment samples were also collected for toxic heavy metals analysis for the laboratory's expanded UNU research project.

At least two duplicate samples were collected at each sampling area.

Surface water samples from bays and from shallow rivers were collected by dipping the sample bottle just under the surface of the water. Surface water samples obtained from bridges and bottom water samples were obtained using the NISKIN water sampler.

Water samples for OCPs and phthalate analysis were collected in one bottle. Water samples for phenols analysis were acidified with 2 ml HCl in a separate bottle. All water samples were cooled in an ice chest while on transit from sampling to the laboratory. The samples were placed in a refrigerator at 4^oC until the time of extraction. The samples were processed within one week from sampling.

Sediment samples from the bay and in deep rivers were obtained using an ECKMANN Dredge. The sediment samples were placed in glass bottles and stored in the freezer until time of analysis

3. Analytical Results

3.1 Summary of Results

The summary of EDC concentrations reported for the samples are summarized in Tables 3.1-3.2.

The summary of averaged concentrations of EDC concentrations of duplicate samples and estimate of standard deviation are listed in Tables 3.3-3.5

The raw data obtained for the samples and the blanks are given in Appendix 1.1-1.3

Selected PCB congeners were analyzed in selected water and sediment samples. The method of analysis for OCPs was adopted for analysis of specific congeners of toxic PCBs. The method performance for analysis of PCBs in water was assessed using spiked samples. The OCPs and PCBs in the sediment samples were prepared for GC/MS analysis by Soxhlet extraction (24 hours with ice - cold condenser) and clean-up with with long alumina/silica column. The OCPs/PCBs were eluted together using 5% acetone/hexane. The performance of the method for the sediments has not been assessed adequately in the laboratory. The summary of OCPs and selected PCB congeners in water and sediment samples collected in Manila Rivers and Bay are shown in Table 3.6

3.2 Summary of Quality Assurance /Control Measures

The calibration curves were prepared using internal standard method as prescribed by the manual. The instrument was set up for SIM analysis following the Shimadzu GC/MS QP5000.

The Quantitative tables used for the analysis of the EDCs are shown in Tables 4.1-4.4. The performance of the analytical methods in the laboratory was assessed by analysis of spiked ultrapure water samples.

For each batch of analysis of 4-10 samples, one blank and one spiked sample were analyzed.

Each sample was analyzed in one determination. For samples that were collected in duplicate, the average of the results of the two samples was reported and the estimate of standard deviation was indicated.

The summary of data pertinent to method performance and quality control is presented in Tables 5.1- 5.7.

3.3 Problems Encountered

1. It had been difficult to see good peaks for the specified target and reference mass fragments of endrin in the standard that was used in the analysis. Thus the signal to mass ratio was very small for the endrin calibration standards. We tried to use a commercially prepared stock mixed standard from SUPELCO but endrin did not also give the desired sensitivity for the target and reference mass fragment ions. It is possible that some high blank concentration for endrin may be due to poor calibration of endrin. GC/MS analysis of endrin could be improved with the availability of good endrin standard.

2. Not all the samples collected during the second sampling were analyzed for phenols because of two reasons.

1. After getting the unsatisfactory results in the samples collected during the first sampling, experiments were done to look at possibilities to improve the recovery for the second batch of samples. After ruling out possible sources of error in the drying of the extract and in the derivatization prior to GC/MS, we decided to do solvent partitioning experiments to assess the efficiency of the recommended extraction solvent. We decided to use an acetone/DCM mixture for the extraction of the samples.

2. The untimely breakdown of the GC/MS did not allow us to finish the phenols analysis on time for the annual report.

4. Conclusions

The OCPs monitoring showed that traces of DDT, endosulfan, heptachlor and gamma BHC were found in Bataan Bay near the Petrochemical Complex. Endrin was detected in highest amount in Calumpang River in Batangas. OCPs found in bottom water generally are higher than in the surface water. Comparing this year's result with that of last year, more types of OCPs were detected this year and higher concentrations are recorded.

Phenols are found in highest amounts in the Manila Rivers. Nonyl phenol concentration was highest in Paranaque river. The excessively large amount of phenol concentration detected in Manila Rivers can be attributed to the lack of efficient sewerage treatment facility in the city.

Comparison of the OCPs and phenols concentrations in the samples obtained during the second and third year monitoring are shown in Figures 1.1 and 1.2.

DEHP, DBP and DEP Phthalates are found in highest concentrations in Manila Rivers. Only DEHP was detected in Manila Bay. DEHP, DEP and DBP were also detected in Bataan and Batangas Bays and their river tributaries but in much smaller concentrations than found in Manila.

Based on the monitoring results, phenols is the most serious EDC problem in the Philippine coastal hydrosphere. The OCPs contamination is also evident, reflecting the continued use of EDC pesticides in the farm areas as shown by the increase in detectible OCPs I Bataan and Batangas waters. Among the areas studied, Bataan and Batangas are closest to farming areas.

The next monitoring activity on EDCs should probably include the analysis of the collected data and probable ecological risk assessment.