Regional Applied Research Effort (RARE): Methods for assessing the water quality degradation through water treatment plants during algae blooms and copper sulfate addition or other algae destruction techniques.

RARE is a research effort between the 10 EPA Regions and our Office of Research and Development (ORD) in Cincinnati, Ohio. The funds are divided among the 10 regions and each year several projects are proposed. Each region will choose their highest priority project. This harmful algae bloom (HAB) investigation was selected as the RARE project in 2014 for Region 8.

CLRMA 2015 Spring Luncheon April 23rd, 2015 Bob Clement, Environmental Engineer/Microbiologist, EPA Region 8 clement.robert@epa.gov

The views expressed are those of the presenter and do not necessarily reflect the views of the EPA

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Region 8’s RARE project on HABs expands on the RARE project in Region 5. Ohio EPA was finding measurable levels of microcystins in Lake Erie. Region 5 proposed a RARE project that would test for HABs at PWSs that were most impacted by algae blooms in Lake Erie. ORD has been conducting research on HABs at these facilities for the past two years.

Because PWSs in Region 8 did not have HAB data. The strategy changed to sampling at more PWSs to determine which systems may have HABs. Of the 18 systems reviewed, 9 systems have been chosen based upon the severity of their algae challenges, to take monthly samples at their raw water sample line starting in May and ending in October.

The systems represent about a 50/50 split between lake and river sources.

The systems added separately or in combination, copper sulfate, peroxide, powered activated carbon, mixing (Solarbees) or plant improvements to address algae problems.

Most of the plants reported taste and odor issues and some reported filter clogging algae problems. The severity of the problems varied from year to year.

Many of the systems that use a river as a source have presed ponds that can decrease the water quality.

Presed pond #1

Backwash pond

Presed pond #2

But lake sources can be even more complicated: Snowmelt can be captured in high mountain reservoirs only to be transferred by open canal to lower quality reservoirs or holding ponds that can decrease the water quality.

What HAB toxins will be tested?

Individual microcystin congeners (microcystin-LA, -LF, -LR, -LW, -LY, -RR,-WR, -YR) and nodularin will also be tested by ultra-high pressure liquid chromatography (UHPLC) coupled with high resolution mass spectrometry (LC-MS).

Total microcystins (liver toxins) and nodularin (liver toxins) by enzyme linked immunosorbent assay (ELISA). There are 80 different congeners of microcystins.

ELISA tends to overestimate the levels of microcystins present and does not provide levels of the individual congeners. Some of which are more toxic than others.

Trace metals: Aluminum Arsenic Barium Beryllium Bismuth Cadmium Chromium Copper Iron Lithium Manganese Nickel Lead Antimony Selenium Tin Strontium Thallium Uranium Vanadium Zinc

Common elements: Calcium Potassium Magnesium Sodium Phosphorus Silicon

Analysis will be by ICP-MS or ICP-AES

Anions: Chloride Bromide Bromate Chlorite Chlorate Perchlorate Flouride Nitrite Nitrate Phosphate Sulfate Sulfer

Other water quality parameters: Ammonia Total alkalinity Total organic carbon (DOC) Total dissolved nitrogen (TDN) Chlorophyll a Total dissolved phosphorus (TDP) Taste and odor compounds: Geosmin & MIB

Anions will be analyzed by ion chromatography or titration; ammonia and total alkalinity by titration; DOC/TDN by catalytic combustion and chlorophyll a by EPA method 445.0.

What kind of scenarios will be represented by these 9 systems?

Lake sources that were once pristine but are now severely impacted by beetle kill.

A river source in Northeast, SD that is impacted by small reservoirs, slow moving streams and agriculture.

A lake source, that for the last 20 years always froze over --until this year.

The upper Missouri River is piped to a large holding reservoir that can’t be drained and cleaned. Both the Missouri River reservoir and holding reservoir are impacted by algae.

The Milk River is a slow moving river that winds through farming communities in the US and Canada and was subject to a drought/flood cycle that led to all of the PWSs on the river being over the disinfection byproducts (DBP) maximum contaminant levels (MCLs). Previous to that climate cycle their DBP levels were half the MCL.

Although this lake has sparse vegetation, it has algae growth year round. They add copper sulfate selectively to sections of the lake.

Lake Sakakawea is used by at least 14 PWSs. This water will proceed through five presed ponds in it’s 100 mile journey to the treatment facility.

Erie Lake is a protected fishery that is also used by a drinking water system. They can do very little to treat the raw water for algae blooms due its protected status. This year they had to lower the lake level for piping upgrades historically, that has always increased the algae problems in this lake that is only 13 feet deep.

This Platte River intake location is impacted by a large WWTP and recreational reservoir five miles upstream, two presed ponds and a back wash recycling pond.

Mountain Dell Reservoir has a golf course adjacent to it and had algae problems so bad one year they couldn’t treat the water. They added a Solarbee (mixer) and reduced their copper sulfate additions from tons to pounds per year.

Is it possible that even with all these different scenarios we will not detect HABs? It is possible! HABs are episodic, it is unknown what environmental conditions start the metabolic machinery to produce toxins, they can vary their height vertically in the water column throughout the day along with many other variables that make detecting them in a single monthly sample difficult. On the other hand, HABs have been detected without any visible sign of a bloom and no taste and odors. By testing more systems we can increase the probability of detecting toxins and know where to perform more extensive sampling in 2016.

What HABs will be tested?

Microcystin (hepatotoxin) LA, LF, LR, LW, LY, RR, WR, YR, There are 80 different congeners of microcystins.

Nodularin (hepatotoxin) LA, LF, LR, LW, LY, RR, WR, YR, There are 80 different congeners of microcystins.

Total microcystins and nodularin by enzyme linked immunosorbent assay (ELISA) Individual microcystin congeners (microcystin-LA, -LF, -LR, -LW, -LY, -RR,-WR, -YR) and nodularin by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS)

Anatoxin A (nerve toxin).

Cylindrospermopsin (liver and kidney toxin).

Fascaplysin (inhibits cyclin dependent kinases which play a key role in cell cycle).

Okadaic Acid (affects mRNA stability). Tautomycin (protein

inhibitor).

Analysis will be by ultra-high pressure liquid chromatography (UHPLC) high resolution mass spectrometry. Detection limits will be in the 50 to 100 ppt level, which meets WHO provisional action Level for microcystins of 1 ppb. Also the ELISA method.

Mycotoxins (Aflatoxin B1, B2, G1, G2, M1) a toxic secondary metabolite produced by organisms in the fungi kingdom.