Sample Methods

Water samples were all collected in West Maui in and around reef systems that were within and adjacent to the burn zone of the Lahaina fires. Samples were collected in impacted areas within the affected burn zone, control sites outside of the burned urban area (Kahekili, approximately 4km to the north of the burn extent, and Olowalu, approximately 8km to the south), Lahaina Harbor, streams, transect sampling, and other opportunistic sampling detailed in dataset. Some autonomous sampling data from before the fire event are also included in the dataset.

All shoreline water samples were collected using a 1.5L niskin bottle that was manually closed. Sites were either off a dock (ei. Harbor site) or swam to with a niskin and CTD in hand. PharMed BPT tubing was attached to the niskin bottle and each sample bottle was rinsed 3 times with sample water before filled. Nutrient samples were placed immediately on ice and were frozen as soon as possible. Carbon chemistry samples were poisoned with mercuric chloride. All samples were placed into a cooler with ice until they were organized at the end of the field collection day.

Transect samples were collected by lowering a 1.5L off of the boat and sampling the same as the shoreline. Metal samples were collected by assembling a 10' polyvinylchloride pole to collect non-contaminated samples away from the vessel.

Boat transect sampling was done twice a day on two dates, 2023-10-07 and 2024-01-27. These were done at sites L1-L15. Between 2023-10-07 and 2024-10-23 shoreline samples were taken for sites SH1-SH11. Between 2023-10-07 and 2024-08-04, an autosampler was used at Kahekili Beach Park (KBP) and Mala Point (M).

Autosampler samples were collected using a custom built device. Tedlar bags were attached to the autosampler channels and were pre-poisoned with mercuric chloride. Some

Sampling Dates

Dates for boat transect sample data: Two time sampling single day samplings for site L1-L15
- 2023-10-07
- 2024-01-27
Dates for shoreline water sample data: Samples were collected in two day intervals from the shoreline of the listed sites (SH1-SH11) in West Maui spanning from Olowalu to Kahekili.
- 2023-10-07 to 2023-10-08
- 2023-11-13 to 2023-11-14
- 2023-11-30 to 2023-12-02
- 2024-01-10 to 2024-01-11
- 2024-01-27 to 2024-01-28
- 2024-05-10 to 2024-05-11
- 2024-08-03 to 2024-08-04
- 2024-10-23
Dates for autosampler data: Samples collected at sites Kahekili Beach Park (KBP) and Mala Point (M) (SH5 and SH8)
- 2023-10-07 to 2023-10-09
- 2023-12-01 to 2023-12-03
- 2024-01-10 to 2024-01-11
- 2024-01-26 to 2024-01-28
- 2024-05-09 to 2024-05-11
- 2024-08-02 to 2024-08-04

Sampling Locations

Stations and locations are listed in the table below.

Site Name	Sampling Method	Latitude	Longitude	Description
LH1	Boat Transect	20.87047	-156.68083	Transect from Mala Point
LH2	Boat Transect	20.85898	-156.69733	Transect from Mala Point
LH3	Boat Transect	20.85047	-156.71147	Transect from Mala Point
LH4	Boat Transect	20.84282	-156.72745	Transect from Mala Point
LH5	Boat Transect	20.83527	-156.74414	Transect from Mala Point
LH6	Boat Transect	20.86227	-156.67637	Transect from Mala Point
LH7	Boat Transect	20.85582	-156.66966	Transect from Mala Point
LH8	Boat Transect	20.84885	-156.66361	Transect from Mala Point
LH9	Boat Transect	20.84178	-156.65714	Transect from Mala Point
LH10	Boat Transect	20.8357	-156.65101	Transect from Mala Point
LH11	Boat Transect	20.83012	-156.6436	Transect from Mala Point
LH12	Boat Transect	20.82372	-156.63602	Transect from Mala Point
LH13	Boat Transect	20.8148	-156.63056	Transect from Mala Point
LH14	Boat Transect	20.80798	-156.62518	Transect from Mala Point
LH15	Boat Transect	20.80434	-156.61567	Transect from Mala Point
SH1	Shoreline Sampling	20.865082	-156.673642	Shark pit
SH2	Shoreline Sampling	20.872221	-156.678991	Ferry pier
SH3	Shoreline Sampling	20.871976	-156.67873	Harbor
SH4	Shoreline Sampling	20.880425	-156.685162	Baby beach
SH5	Shoreline Sampling	20.883216	-156.687382	Mala point
SH6	Shoreline Sampling	20.887829	-156.684862	Mala Tavern
SH7	Shoreline Sampling	20.902508	-156.684888	Wahikuli
SH8	Shoreline Sampling	20.936749	-156.692258	Kahekili
SH9	Shoreline Sampling	20.809339	-156.607049	Olowalu beach
SH10	Shoreline Sampling	20.885432	-156.686466	Kahoma outflow beach
SH11	Shoreline Sampling	20.860466	-156.667369	Kauaula stream bridge
Kahekili Beach Park (KBP)	Autosampler	20.93727	-156.69351	Kahekili Beach Park (KBP)
Mala Point (M)	Autosampler	20.883216	-156.687382	Mala Point (M)

Sample Analysis

a. Carbon Chemistry (μmol/L): One sample is collected for the analysis of TA and DIC and a second is collected for DOC. TA/DIC is collected by submerging a niskin bottle just below the surface of the water and collecting a sub sample. A piece of PharMed BPT tubing is attached to the niskin bottle and placed on the bottom of a 250mL VWR narrow mouth glass bottle and rinsed and dumped three times. Each sample is poisoned with 0.1 mL of mercuric chloride and the glass topper is sealed with Apiezon L Vacuum Grease and a snap-grip clamp.

a.1.Total Alkalinity (TA): Alkalinity determination using the Gran titration method. Alkalinity is determined by the amount of acid (in mol/kg or mol/L) needed to titrate a water sample to the CO2 equivalence point (about 4.4) at which all inorganic carbon species are converted to CO2 in seawater. Measurements validated with Dickson CO2 Certified Reference Material.

a.2. Dissolved Inorganic Carbon (DIC): All species of carbon are transformed into CO2 and the resulting CO2 gas is purged from the water sample by the pure nitrogen (N2) carrier gas and use only a single certified reference material to make a three-point calibration line or broken line. Apollo Dissolved Inorganic Carbon Analyzer Model AS-C5 was calibrated with Dickson CO2 Certified Reference Material.

a.3. Dissolved Organic Carbon (DOC): Water for TOC analysis was collected in 40 mL amber Volatile Organic Analysis (VOA) vials with silicone septum caps. TOC was measured on a Shimadzu TOC-L Combustion analyzer. Water samples were not filtered prior to collection and included both dissolved and particulate organic carbon.

a.4 Total Organic Carbon (TOC): Water samples were analyzed for total organic carbon (TOC). Water for TOC analysis was collected in 40 mL amber Volatile Organic Analysis (VOA) vials with silicone septum caps. Prior to sampling, vials and caps were acid washed with 10% HCl and vials were combusted at 450°C for 4 hours. Prior to collection, sample vials and caps were triple rinsed with sample water. Vials were filled to the shoulder with sample water and then acidified to a pH of ~2 via dropwise addition of 12M hydrochloric acid.

b. Trace Metals: Samples for dissolved and total dissolvable metal concentrations were collected in acid washed polyethylene bottles, which were rinsed 3 times before filling. During offshore sampling, a 10' polyvinyl chloride pole was assembled to collect non-contaminated samples away from the vessel. During shore sampling, bottles were filled from upstream waters and closed immediately after filling. Samples for dissolved metals were vacuum filtered using a 0.2 um polyethersulfone membrane. Samples for total dissolvable metals were not filtered. Both filtered and unfiltered samples were acidified to a pH of 1.8 using ultra high purity hydrochloric acid and stored for several weeks prior to analysis.

For dissolved iron, zinc, nickel, copper, cadmium, and lead, samples were subject to preconcentration using a SeaFAST S2 system (Elemental Scientific) after addition of an isotope spike to track sample recovery. 10 mL of samples were preconcentration into 0.75 mL and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using an iCAP-TQ instrument (Thermo Fisher Scientific) using O2 as a collision gas. Pre-concentration blanks were assessed by measuring high purity (18.2 M-Ohm cm-1) water after passing through the SeaFAST system and subtracted from measured values.

For dissolved Mn, Ba, V, and As, and all total dissolvable measurements, samples were also measured by ICP-MS, but after dilution in 0.1 M nitric acid with In as an internal standard. These samples were calibrated diluted multi-element standard (Inorganic Ventures) with matrix-matched seawater collected from offshore waters in the North Pacific Subtropical Gyre.

For dissolved metals analyzed by both procedures, CASS7 and NASS5 seawater reference materials were measured to ensure accuracy of calibrations. No standards are available for total dissolvable metal measurements.

c. Metabolomics: For untargeted LC-MS/MS, 200 mL water samples were acidified to pH2 and collected on solid phase extraction cartridges with a 60mg HLB resin bed. Cartridges were eluted using 2 mL of LC/MS grade methanol, evaporated to dryness, and redissolved in 100 µL of 80:20:1 Methanol/water/formic acid. Samples were run in data dependent acquisition mode on an Orbitrap Exploris MS/MS coupled to a Vanquish Flex UHPLC using a Kinetex® 1.7 µm C18 150 x 2.1 mm Column and C18 guard column.

d. Nutrients: Nutrient samples were collected by rinsing a previously acid washed 125 mL Nalgene HDPE bottle three times with surface water and next filled leaving room on the top to allow freezing. Samples are immediately placed in a dark cooler on ice and frozen at the end of the sampling day. Samples are removed from the freezer the night before analyzing and are slowly defrosted in a dark environment. Measurements were validated with Kanso Certified Reference Material.

d.1. Nitrate and Nitrite: Method no. A-044-19 Rev.5: Nitrate is reduced to Nitrite at pH 7.5 in a copperized cadmium coil. Nitrite is reduced with sulfanilamide to form a diazo compound that then couples with N-(1-Naphthyl)ethylenediamine dihydrochloride to form an azo dye that is measured at the absorbance of 540 nm.

d.2 Phosphate: Method no. A-005-19 Rev.3:ortho-phosphate, molybdate, and antimony form a blue color followed by the reduction with ascorbic acid at pH <1. This reduced blue phospho-molybdenum complex is read at the absorbance of 880 nm.

d.3 Silicate: Method no. A-006-19 Rev.4: silico-molybdate is reduced in an acidic solution of molybdenum blue by ascorbic acid. Oxalic acid is added prior to ascorbic acid to reduce interference from phosphates.

d.4 Ammonia: G-327-05 Rev 9: sample is reacted with o-phthalaldehyde at 75 °C with a borate buffer and sodium sulfite and analyzed at an absorbance of 460 nm following excitation at 370 nm.

e. Fluorescence Dissolved Organic Matter (fDOM): Water for fDOM analysis was collected in acid washed 20 mL glass vials with urea caps. Vials and caps were triple rinsed with sample water prior to collecting each sample and stored at 4 °C. 3 ml subsamples were transferred into 1 cm quartz cuvettes, which were then loaded into the fluorometer. Excitation-Emission Matrices (EEMS) were generated with excitation values ranging from 240 nm to 500 nm and emission values were measured ranging from 250 nm to 825 nm. These included M:C (Burdigee et al. 2004), FI (McKnight et al. 2001), BIX (Huguet et al. 2009), HIX (Zsolnay et al. 1999), M, A, C, T, and B (Coble 1996).

f. Flow cytometry: Water samples were analyzed for bacterial counts using flow cytometry. Water for flow cytometry was subsampled from triple rinsed and acid washed 1L polycarbonate bottles. For each sample, a 1 mL subsample was transferred via pipette to a 2mL screw cap tube. Samples were preserved with17 µL of 32% paraformaldehyde, for a final concentration of 0.5% paraformaldehyde in each sample. During field collection, samples were stored on ice in the dark. To avoid repeated freeze-thaw cycles, flow cytometry samples were preserved at 4°C for a period of up to 48 hours while in the field prior to long term storage at -80°C. For analysis, 275 µL aliquots from each sample were transferred to 96-well optically clear flat bottom plates. Each sample was stained with 7 µL of Hoechst stain following Selph (2021). Samples were analyzed on a CytoFlex flow cytometry. Gates were established empirically to generate counts of 4 distinct populations of marine microorganisms: heterotrophic bacteria, large autotrophs, small autotrophs, all autotrophs.