-  try detergents

The concentration of petroleum hydrocarbon is reducing with time span of one year. But still pollution is there.

"The FROG-4000TM instrument analyzes air, water or soil to identify

volatile organic chemicals (VOCs) present in a sample and

determine their concentrations".- It cannot measure the oil pollution in groundwater. Only a small portion of oil dissolves in water and due nitrites it will be eaten away by micro organisms in water. The Top floating oil will remain on top with may be little more oil dissolving in water.  Due to the higher ambient temperature the said volatile compounds would have evaporated over the long time from time of oil pollution took place to the time when measurements were made with water samples .

Best way is to test the top oil layer of floating oil only in a well and test same ( Not the water but the oil only using FROG 4000 if this is still available in Jaffna). Comparing this out put with a sample of waste found in or near the Power station will prove the fact this floating oil in well came from this power plant wastes.  

From pictures videos of the polluted wells and with my long experience having dealt with HFO fueled Large Diesel engines I am sure this floating layer is waste oil from such power plant. It is not only waste lube oil it can be the wax and other impurities that come as effluents on filtering of HFO before being sent to the engine. Due to long haulage and storage HFO ends up with much items unsuitable for the engines and these are filtered out by use of special delaval filters which continuously filter in the HFO and stored in hot in a daily service tank for use by engines.  Repeated cooling and heating of these tanks causes condensation and separation of wax etc from HFO which have to finally filtered again just before reaching the engine Injectors. All these operations produce large quantity of wastes and these must be stored with records and be disposed properly with records of who it was transported out and who took same out and how they environment friendly disposed. This is a requirement for the licence to operate the plant.

"Marine Fuel Oil Contaminants

3.1 Water

Water, considered here as a fuel oil contaminant, is the water introduced into the fuel through salt or fresh water intrusion during shipment, or as a result of condensation during prolonged storage. For residual fuels, water content may be determined by distillation (ASTM D-95), or by a centrifuge method (ASTM D-96) which determines the combined water and sediment content, or by titration (ASTM D-l744). Water content of a tanker- or barge-delivered product may occasionally be above specified limits as a result of direct sea water contamination. Fresh water contamination may also cause an additional problem as a collector of water soluble metals and salts present in a heavier fuel. Water, especially salt water, is objectionable in diesel fuel as it may cause injector and piston groove deposits and corrode engine components. Operators of diesels that burn residual fuel or blends centrifuge these fuels to remove water and sediment. Salt water is the greatest single cause of fouling, deposits and corrosion, especially in the higher temperature areas of a diesel. Salt water can also cause excessive separator sludge volume as a result of water/sludge emulsification during centrifuging.

Water can provide the beginning for microbial growth in heavy fuels. These very simple life forms live in the water and feed on the heavy fuel at the water-fuel interface. The result of microbial matter in the fuel can be a slime, which is sometime corrosive, that will foul strainers, filters and separators. The short range solution would be to add a “biocide” chemical additive to the fuel to kill the growth.

The much preferred, long range solution would be to regularly drain the tank bottoms to eliminate the

water, without which this growth cannot exist.

Section 3 Marine Fuel Oil Properties and Characteristics and Their Impact

on the Diesel Engine

3.3 Sodium (Na)

Sodium is an alkaline, metallic element that is found in the combined form of common salt, NaCl. It is extremely active chemically. The sodium found in fuel can come from several sources. But most of it is a direct result of storing and handling procedures from the time the fuel leaves the refinery until it is delivered to bunkers. Salt water contamination in barges used to transport the fuel is not uncommon. To some extent, even salt air condensation in fuel tanks contributes to the overall sodium content. Regardless of the manner of contamination, sodium in fuel is usually water soluble and can, therefore, be removed with the centrifugal separator.

Sodium acts as a paste (flux) for vanadium slag. When unfavorable quantities of vanadium and sodium are present in a fuel they react at combustion temperatures to form (eutectic) compounds with ash melting points within operating temperatures. In molten form sodium/vanadium ash can corrode

alloy steels, and when this condition is allowed to persist unchecked, high temperature corrosion,

overheating, and eventual burning away of exhaust valves, valve faces, and piston crowns is not

uncommon. This sodium/vanadium ratio and its relationship to ash melting temperature are shown in

Section 3, Figure 5.

The chief corrosive constituents in heavy fuel, oil ash formed during combustion are vanadium pentoxide, sodium sulphate, and other complex forms of these primary compounds. The chemical nature of these compounds and their interaction with steel surfaces on exhaust valve seats are of real

concern, as the relatively low melting points of most of these compounds make them very corrosive at

normal engine exhaust temperatures. The thickness of the various oxide layers depends on the temperature and the exhaust gas composition. In their molten states, the vanadium-sodium-sulfur

compounds also act to dissolve the exhaust valve surface ferric oxide (Fe203) layer, thus exposing the underlying steel surface to further oxidation attack and subsequent erosion.

The oxidation attack takes place by two mechanisms: gas phase oxidation and liquid phase oxidation.

In the gas phase oxidation, the high temperature oxygen-containing exhaust gases react with steel to form oxides. Liquid phase oxidation (corrosion) takes place when molten sulfates and pyrosulfates in the exhaust gases deposit on valve surfaces. In extreme situations, similar sodium/vanadium ash corrosion attack can also occur downstream of the exhaust valves in the turbocharger exhaust gas turbine and blading.

3.5 Sediment

Sediment is another contaminant which finds its way into marine bunkers. Rust, scale, weld slag, dirt

and other debris can be introduced in storage or in pipeline or barge transport. The majority of this sediment can be removed by settling, straining or filtration, or centrifuging in the shipboard fuel oil system.

As the specific gravity and the viscosity of fuel oils increase, the sediment level, which originates primarily from transport and storage contamination, will increase as a result of a slowing of the natural settlement process. As both the water and sediment content of heavy fuel oil increase, the usable energy in the fuel decreases. Usually, if sediment (and water) exceed one percent (1%), most oil suppliers will adjust bunkered fuel cost to compensate the buyer. However, since sediment (and water) contamination frequently occur during storage and fuel transport over water, the buyer must accurately and continuously sample the fuel oil during bunkering to obtain a representative bunker

sample to be assured he is getting what he is paying for. Sediment (and water) can be settled out to a large degree during heated storage. However, as the specific gravity of heavy fuel oil approaches that of water, the settling process becomes less and less effective. The effectiveness of purification/clarification treatment also is reduced. Sediment removal is essential to reduce high ash or particulate contamination of a fuel since both can contribute to increased deposits, corrosion or abrasive wear. 

Section 3 Marine Fuel Oil Properties and Characteristics and Their Impact

on the Diesel Engine 

3.7 Alumina/Silica

Hard, abrasive particles, such as alumina/silica catalyst carry-over, originate in the refinery when this

powdered catalyst is added to the charge stock of a fluidic catalytic cracking (F.C.C.) unit. Due to erosion and fracture, some of the catalyst is not recovered but is carried over with the bottoms from the F.C.C. unit. Larger sized catalyst particles, greater than ten (10) microns, also can be carried over if there is a defect in the catalyst removal equipment (such as cyclone separators), if there is an upset

in the operation of the F.C.C. unit, or if the heavy (low API gravity) bottoms (containing catalyst

particles) are not permitted sufficient time to settle-out in heated storage (when this method is used to control catalyst carry-over).

It is also possible to contaminate a clean marine residual fuel oil with catalyst particles during transport. For example, if steamship fuel (frequently containing catalyst particles) has been transported by barge prior to moving a clean heavy fuel oil for a diesel powered ship, the barge bottom sediment will be mixed with the clean fuel oil and will contaminate it.

Section 3 Marine Fuel Oil Properties and Characteristics and Their Impact

on the Diesel Engine 3

Because cat-fines are generally small, very hard, and quite abrasive to pumps, atomizers, piston rings and liners, a number of major diesel engine builders have concluded that thirty parts per million (30 ppm) of alumina in the bunkered fuel oil is the upper limit for successful treatment and engine operation. The average particle size, as well as the concentration, greatly impacts the wear rate of engine components. Small sized catalyst particles, in the one to ten (1-10) micron range, typically cause accelerated wear in injection pumps and injectors and only moderate increases in cylinder assembly wear, such as piston rings, piston grooves, and liners. The larger sized catalyst particles, in the ten to seventy (10-70) micron range, typically cause very accelerated wear rates in the cylinder assembly area. Accelerated damage can also be expected on injection pump inlet valves, exhaust valve seating areas, and turbocharger turbine blading. These larger sized particles have been associated with catastrophic wear rates.

3.9 Sludge

Sludge is a contaminant that results from the handling, mixing, blending, and pumping of heavy fuel while stored at and after it leaves the refinery. Storage tanks, heavy fuel pipe lines, and barging can all contribute to the sludge. Water contamination of a high asphaltene fuel oil can produce an emulsion during fuel handling which can contain more than fifty percent (50%) water. Shipboard transfer pumps frequently can provide the necessary energy to produce emulsified sludges during normal fuel transfers. These emulsified sludges can cause rapid fouling and shutdown of centrifugal purifiers and clogging of strainers and filters in the fuel oil system, and rapid fouling if burned in the engine.

3.11 Fibers

Fiber contamination can cause significant problems in fuel handling aboard ship. This type of contamination usually occurs during transport and storage. Fibers can plug suction strainers protecting pumps within minutes of initial operation. Whereas cleaning strainers is not a difficult task, the frequency of cleaning and the need for round-the-clock attention generally create problems. A centrifuge normally is ineffective in removing oil soaked fibers because they have the same density as the oil being purified. Hence, downstream manual or auto-strainers and fine filters can be expected to clog in a short period of time and continue to clog frequently until the entire amount of a fiber contaminated fuel has been consumed or removed.

3.13 Oxidation Products

This form of contamination is the result of the marine residual fuel aging, either before or after it is bunkered. Residual fuels are not stable for long periods of time at elevated storage temperatures. The elapsed time from the refinery to use onboard, ideally, should be less than three (3) months. Further, it is anticipated that future residual fuels resulting from more intense secondary processing will be even less stable. Heated heavy fuels, stored in uncoated steel tanks and exposed to air (oxygen) oxidize and polymerize with time. The resultant sludges, gums and resins will initially form in solution and then agglomerate and settle or adhere to the tank’s surfaces. Also, as heavy fuels age, their shipboard conditioning and treatment become more difficult. In the extreme, the diesel engine’s Combustion process can deteriorate causing increased fouling, deposits and corrosion as a result of burning such partially oxidized older fuel oils. Generally, residual fuel oils should not be bunkered and utilized as ballast, trim, or held in reserve for extended periods of time. The oldest fuel on the ship should be burned first to prevent any heavy fuel oil from aging beyond three (3) months from its bunkering date." From NOTES ON

HEAVY FUEL OIL Please see attachment.

http://powerplants.man.eu/fuels/hfo

http://www.wartsila.com/docs/default-source/Power-Plants-documents/w%C3%A4rtsil%C3%A4-50df.pdf?sfvrsn=2

http://www.defiant-tech.com/pdfs/FROG-4000%20Manual%202014%20Vol4.pdf

Thanks for sharing very good conducive comments and documents

APPENDIX II: DETECTABLE CHEMICALS CONTINUED from

FROG-4000TM User’s Manual

It is not clear that this hand held instrument could measure all the pollutants that comes from waste HFO and the special Lube oil used in this NPC power station. All possible wastes are shown in earlier posting. More details will follow.

http://www.defiant-tech.com/pdfs/FROG-4000%20Manual%202014%20Vol4.pdf

The hydrocarbons mostly found in marine fuel oils fall into four (4) main classes − paraffinic, aromatic, naphthenic and olefinic. These basic compound

types are further categorized below.

Paraffinic hydrocarbons (CNH(2N+2)) are lower in specific gravity than aromatic hydrocarbons of the same boiling point, while naphthenic and olefinic compounds are intermediate in density. Their resistance to chemical change or oxidation is very good. These hydrocarbons are clean burning, and thus are desirable in distillates such as gas oil or diesel oil.

Aromatic hydrocarbons (CNH(2N-6)) possess a much higher specific gravity than the other three classes. Aromatics are very stable under heat and are chemically active to a moderate degree. The aromatic compounds contain a higher proportion of carbon than the other hydrocarbon types. Due to this characteristic, they have a tendency to smoke, which somewhat limits their use in diesel engines.

Naphthenic hydrocarbons (CNH2N-ring type) are extremely stable, cyclo-ring compounds and in many cases have more stability than the paraffins. These hydrocarbons are more commonly found in heavy marine fuel oils rather than distillate oils.Olefinic hydrocarbons (CNH2-straight chain) are more chemically active than the other three classes of hydrocarbons. Olefins are subject to oxidation or polymerization, forming gums. Olefins are not present in large amounts in straight-run distillates, but are found in large quantities in cracked marine fuel oils.

While crude oil is the source of the various hydrocarbon compounds in marine fuels from which thermal energy is produced during combustion in a diesel engine, it also is the source of many undesirable properties and characteristics which are carried over in the refining process to the resultant petroleum product. Section 2, Table 1 lists the principal contaminants which are related to the source of the crude oil. These contaminants will be concentrated in heavy fuel oils which have been subjected to intensive refining

Just using a simple test for "OIL" just testinting BTEX will not be sufficient to tests the WASTE OIL found in Chunnakam well water.

In addition to above the wastes from the Special Lube oil with higher TBN value will have lube oil with added materials to provide lubrication and these used lube oil will contain dissolved heavy metals that could come from the machines parts bearing Pb, Piston rings Cr and other special metals depending on the make of machine Piston liners same as above and with the frequent failures experienced by the very old machines every time major failure occurs the manufacturers require compleate lube oil change as much of defective components would have spoilt the lubricating properties of the lube oil. It is my estimate from the number of units generated by the plant details publicly available from the generation reports maintained by PUCSL in their web site. This is shown in the figure attached.

Limitations

 Although many consider GC/MS to be the "gold standard" in scientific analysis, GC/MS does have some limitations.  Because great faith is maintained in GC/MS analysis, erroneous results are not expected and hard to dispute.  However, false positives and false negatives are possible.

    Some problems with GC/MS originate in improper conditions in the GC portion of the analysis.  If the GC instrument does not separate the specimen's compounds completely, the MS feed is impure.  This usually results in background "noise" in the mass spectrum.  If the carrier gas in the GC process is not correctly deflected from entering the MS instrument, similar  contamination may occur.

    Also, the MS portion suffers from the inexact practice of interpreting mass spectra.  An analyst must correlate computer calculations with system conditions.  The typical memory bank for MS identification contains about 5000 spectra for a particular group of compounds.   Even if a competent analyst could find conclusive results pointing to one substance out of 5000 substances, this does not rule out the remaining over 200,000 known existing chemicals.   For the 5000-spectra memory bank, the typical computer result is limited to as many as six possible identifications.

    In one instance, erroneous GC/MS results may have been responsible for a criminal defendant receiving a death sentence.  John Brown killed a police officer and wounded two bar patrons in a shoot-out on June 7, 1980 in Garden Grove, California.   Mr. Brown's diminished capacity defense to capital murder relied on the assertion that Mr. Brown was under the influence of narcotics at the time of the shooting.   The prosecution introduced GC/MS evidence that showed Mr. Brown's blood to be free of narcotics.   The California Supreme Court overturned the jury's death sentence because the prosecution never introduced evidence from a radioactive immunoassay ("RIA") test that detected phencyclidine (PCP) in Mr. Brown's blood.   Obviously, an example like this demonstrates that analytical evidence, including GC/MS, should always be confirmed with another reliable technique.

    A more advanced analytical method is MS/MS, a tandem series of instruments, which has the advantage of increased sensitivity.   One court states that MS/MS analysis has never produced a false positive in the FBI laboratory.   However, MS/MS is not widely used yet as the instrument's cost is prohibitive.

Conclusion

    GC and MS are useful tools for chemical analysis, especially when used together.  An attorney can present an effective attack or defense of GC/MS evidence with a basic knowledge of the analysis process and an insistence on documentation of important indicators that may affect GC/MS results.  At the minimum, a technician must process standard samples before and after analyzing a specimen in question.  In litigation an adverse party should seek hard copy output, including system conditions.  Finally, no analytical technique produces results that are completely without doubt.  An effective advocate should always seek corroboration of GC/MS results.

Notes om Gc used by us several years back is attached. as we used this in late 1960 in the mechlab in UOP.-- The gas chromatograph makes it possible to separate the volatile components of a very small sample and to determine the amount of each component present the non volatile components are not tested/detected.( The waste oil contain much non volatile components. )

Added the complete solutions for the analysis of anions, cations, metals, and organic contaminants.These contaminants affect water quality in many ways, including taste, toxicity, and odor. Knowledge

List of these contaminants helps you to monitor your water process so that you can understand source contamination and treat water in the most economical way possible - 

f trace elemental analysis solutions, including atomic absorption (AA), inductively coupled plasma–optical emission spectrometry (ICP-OES), and inductively coupled plasma–mass spectrometry (ICP-MS) for accurate, effortless identification of trace level elements. Environmental applications require instruments that can handle high sample throughput and demanding detection limits.

Ion Analysis

Ion chromatography (IC) is now a well-established and accepted technique for the monitoring of anions in environmental waters, such as surface, ground, and drinking water 

To investigate the biodegradability of oil in sand by microbial blends, a laboratory experiment was conducted at the Department of Biology of NTNU using two microbial blends. The two commercially available microbial blends, CS2 and PetroClean, were tested for their ability to accelerate the biodegradation of oil in sand under different temperatures and (simulated) weather conditions. They were evaluated regarding to their degradation efficiency and time with cost being considered as a prevailing factor. The bacterial blends were kindly provided by the Alabaster Group’s official distributor in Norway, NK Gruppen. ---  The chemical formulas and contents of those blends were not provided by the manufacturer but the “material safety data sheets” (MSDS) mentioned they presented no hazards to health, safety or environment. 

6.2.4.4. Discussion of the results and conclusions

What we can retain from this experiment is that the natural biodegradation of oil in the sand is definitely taking place, although we cannot confirm it is accelerated by the microbial blends as we see effects but the time is too short (just three weeks) to be sure of their efficiency on long term and the results’ uncertainty is quite high. If we follow the results displayed earlier, we can say that CS2 is quite efficient at low and medium temperatures while Petroclean seems more efficient at medium to high temperatures. The action of biodegradation occurs at the level of the long-chained hydrocarbon molecules that are broken up into smaller fractions. In real field conditions, it is very important to maintain the soil moist (at least 25%) for an optimal efficiency according to the manufacturer recommendations.

HENCE BIODEGRADATION TAKES PLACE WITH TIME AND MEASURING THESE VOLATILE COMPOUNDS AFTER A PERIOD OF TWO YEARS FROM THE TIME THEY APPEARED IN THE WELLS SERVES NO PURPOSE COMPLETE WASTE OF TIME MONEY AND IT IS A BIG WHITE WASH TO PROVE THE POWER PLANT DID NOT POLLUTE WITH WASTE O.

https://www.thermoscientific.com/content/dam/tfs/ATG/CMD/cmd-documents/bro/bro/chrom/market/XX-43082-Product-Portfolio-Drinking-Water-Analysis-XX43082-EN.pdf

https://www.ntnu.edu/c/document_library/get_file?uuid=35503807-a589-477f-a2c6-8dd19b47dab4&groupId=163835

Thanks ...  I will let you know soon .. 

Checked up with the Retired Government Analyst - Kandasamy who is in Calgary - He said you can repeat a controlled experiment testing oil/water sample as it is with another sample of oil/water to which Nitrite is added and use the FROG 4000 if it is still there available for you to test out will show the results. This is the direct answer to your question. -- 

this article also helpful

https://eurekamag.com/research/004/000/004000000.php