Original Water sampling

Equipment Cleaning and Preparation

A. Water Sample Bottles (Stream Lab. protocol)

1. DIRTY WATER SAMPLE BOTTLES SHOULD BE EMPTIED, THE LIDS REMOVED, AND PLACED IN THE "DIRTY UNBREAKABLES TO BE ACID WASHED" BASKET BY THE USER.

2. Any bottles appearing stained on the inside or cracked should be discarded.

3. Using 10% HCl, wet all surfaces thoroughly, rinse in bin of distilled water, then

rinse 4X under a stream of distilled water.

4. NEVER SCRUB WITH A SCRUBBER.

5. Drip dry in cart.

6. Replace clean lids and bag in seal-able plastic bags.

B. Protect any other pieces/parts of equipment that will come into direct contact with the sample (place bottles in seal-able plastic bags for storage and transport to field).

C. Calibrate the field conductivity meter with the appropriate standard(s).

D. Go through field equipment check list, which is as follows:-

-wading and extension rods

DH81 connector, cap and nozzles (plus one extra)

3 liter Nalgene sample bottles (2 per site)

measuring tape

bucket

chest waders

60 ml syringes for pH and red vial caps (3 per site)

DIC vials (3 per site)

DOC vials (3 per site)

conductivity meter

field forms and clipboard

wash bottle with nanopure water

coolers and ice

KEY for CAP canal gate

disposable 95 x 16.8 plastic NH4 vials / caps (3 per site)

Field Procedure

Rinse all sample collecting equipment and all vials 3 times with water from the edge/side of the channel before sampling.

There are 3 methods for sampling, listed in order of preference. However the method used should be chosen according to site and flow conditions – IF the water is too deep/fast flowing NEVER WADE OUT INTO THE CHANNEL. If you are in ANY DOUBT about the conditions DO NOT WADE – collect a sample from a safe place at the side of the channel.

Cross-channel depth-integrated sample (CWDI) - place tape across channel section to be measured. This should be a straight-sided wade-able section of stream, with reasonably smooth, laminar flow; sections with stagnant or very turbulent water flow should be avoided. Collect water sample using the DH-81 equipment at equal-width-increments (EWIs) across the channel. The stream-width should be divided into a number of equal-width intervals; use 5 to 10 intervals for cross sections less than 5 ft wide and a minimum of 10 increments in streams 5 ft wide or greater, up to a maximum of 20 increments in extremely wide, shallow cross sections. The sample verticals should be spaced at least 6 in. apart. At each point one continuous, down-up transit of the stream should be performed at a constant rate, with no pause when the channel bottom is reached. Choose a nozzle size based on the requirement to collect the volume of sample required from the whole channel width, taking into account the channel width, depth and flow rate. DO NOT allow the bottle to overfill – this could lead to enrichment of heavy particles and bias the sample. If you do not have enough water after the first complete cross-section, you must repeat the procedure over the ENTIRE cross-section. If a bottle becomes almost full BEFORE you have finished the sample, detach it and use a new second one. Then composite the entire sample by placing both through the cone splitter in the lab.

Depth-integrated sample (DI-only). If you have access to a reasonably straight-sided bank and the water at the edge of the channel is fairly deep (2 feet or more) and fast-flowing, use the DH-81 sampling rod(s) and bottle to take a depth-integrated sample from a point near the bank. Lower and raise the sampler repeatedly at the same point as described above, until enough sample has been collected.

Dip sample (Dip). A dip sample will need to be taken from the surface when the water is too fast to enter (above the knee), and there is not a vertical bank from which a DI-only sample can be taken. If the dip sample can be taken from the center of the stream from a bridge spanning the stream using a bucket or Van-Dorn sampler, this is preferred to a dip sample taken from the bank.

4. Take 3 disposable 95 x 16.8 mm plastic disposable vials and caps out with you into the flowing water. Invert and rinse the vials / caps three times before submerging the three vials under the flowing water surface to collect the NH4 sample. Cap the vials under the waters surface. Place the samples into a plastic baggy and store in the ice filled cooler for transport back to the lab. (N.B. We no longer need to collect field-filtered DOC samples).

5. Take 3 x 60ml syringe samples for closed pH. Flush each syringe 3 times from the centroid of flow; before expelling the flush water hold the syringe vertical and tap to release any air bubbles. Take care to expel the last portion of each flush UNDER the surface of the water. Draw the final sample slowly into the syringe from 10cm depth below the water surface (i.e. wrist depth) and place a red stopper over the end of the syringe UNDER THE WATER.

Take 3 vials for closed DIC analysis from the centroid of flow at a depth of 10cm below the water surface. Screw on the vial cap UNDER THE WATER.

7. Measure water temperature and conductivity at 5 points across stream channel, including centroid of flow. Also take air temperature in shaded, sheltered place, not directly adjacent to warm surfaces e.g. side of truck. Place samples on ice.

Laboratory Sample Preparation and Analyses

Sample splitting and filtration

Set up the ‘Dekaport’ cone splitter on a bench top; check it with the level bubble (a level splitter is critical to performance). All Teflon tubes leading off the splitter should be approx. the same length.

Rinse the splitter with some of the appropriate rinse water, then place 10 x 500ml bottles under the outlet tubes and rinse once again, including the collection bottles.

Agitate the sample (for 10 to 15 seconds) to resuspend the sediments. Invert the bottle and rapidly pour into the cone splitter reservoir. Maintain a head of water above the stand pipe to prevent air from entering the splitting block. If the sample consists of more than one bottle full of water, pour all additional bottles through the splitter before finishing. This way the sample is both composited and split into equal components.

The splitting procedure generates 10 equal sub-samples. These are processed as follows:

i) one unfiltered for laboratory specific conductivity (using meter)

ii) three filtered (using 47 mm diameter GF/F ashed at 500 o C) for total suspended solids TSS(gravimetric determination on 104 oC air-dried filter)

total dissolved solids TDS (using pan evaporation method)

total volatile solids TVS (using ashing of the remains from the pan evaporation)

DOC (40ml of filtrate are placed glass vials and analyzed within 24 hours on the Shimadzu TOC 5000)

iii) three filtered (using 47 mm diameter Supor membrane disc filters, filtrate collected in 125ml bottles and analyzed for anions:

TDN (25 ml for persulphate digestion and spectrophotometer)

TDP (25 ml for persulphate digestion and spectrophotometer)

nitrate, phosphate, chloride, (10 mls each for TRAACS) plus ammonium (non-preserved TRAACS method)

major ions e.g. sulphate, chloride (100 ml for IC)

iv) three filtered (using 47 mm diameter Supor membrane disc filters, filtrate collected in 125 ml bottles and analyzed for cations and metals:-

major cations (Ca, Mg, Na, K) analyzed using FAA

metals (Cu, Pb, Zn) remaining filtrate is transferred to nitric acid washed 125 ml bottles and stored in the cold room for eventual analysis by ICP-MS.

pH measurement

Samples should be measured at lab temperature. On returning to the lab take the sample syringes out of the cooler and allow them to warm up to room temp.

Then follow the procedure outlined on the attached sheet.

General Lab. Procedures

A. General Glassware Washing (Stream Lab. protocol).

1. All water chemistry glassware is to be washed with 10% HCL on the same day that it is used. Wear protective clothing.

a) REMOVE ALL REP. NUMBERS WITH ACETONE PRIOR TO WASHING (this does not include labels specifically marked NH4-N, NO3-N, or SRP).

b) Wet all surfaces with acid--check for any residue, scrub if necessary with test tube scrubber.

c) Rinse in bin filled with DISTILLED WATER (keep a constant flow of distilled water into bin).

d) Rinse under stream of distilled water 4X.

e) Drip dry in "clean acid washed glassware" cart--only small objects should be dried on Kimwipes.

f) Return glassware to acid wash cabinet in LSC026.

2. If same day acid washing is impossible, rinse all glassware and fill all vessels with distilled water. Place all glassware to be washed in acid wash room.

3. All glassware is to be washed (rinsed and scrubbed if necessary) in DISTILLED WATER ONLY. NO SOAP EVER!!

4.All pipets and burets should be submerged in 10% HCL in pipet canister, then rinsed with distilled water in the pipet washer 6X.

Chemical water analysis

soil is oven dried at 60 degrees C before KCl extraction and CHN analysis

for detailed protocols of chemical analysis please see: http://www.asu.edu/gel