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   set  data   graph     files  public Amino acid enantiomeric ratios (D/L) of high and low molecular weight (HMW, LMW) DOM
collected from the North Pacific Subtropical Gyre and Central North Atlantic
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The Dataset's Variables and Attributes

Row Type Variable Name Attribute Name Data Type Value
attribute NC_GLOBAL access_formats String .htmlTable,.csv,.json,.mat,.nc,.tsv
attribute NC_GLOBAL acquisition_description String Sample Collection
Samples were collected on two separate research cruises aboard the R/V Kilo
Moana in August 2014 and May 2015. Sampling was conducted at the Hawaii Ocean
Time Series Station ALOHA (A Long-Term Oligotrophic Habitat Assessment;
22\u00b0 45'N, 158\u00b0 00'W) and the Bermuda Atlantic Time Series Site
(BATS; 31\u00b0 40'N, 64\u00b0 10'W) in the Central North Atlantic.

Surface water was sampled via the vessel's underway sampling system. The
intake pipe is situated on the forward starboard hull section of the vessel
approximately 7.5 m below the waterline. The laboratory seawater tap was
allowed to flush for 2 hours prior to each sampling. Seawater was pre-filtered
through 53 \u00b5m Nitex mesh, and pumped through a 0.2 \u00b5m
polyethersulfone (PES) cartridge filter (Shelco Filters, Micro Vantage, water
grade, 9.75\" DOE, polycarbonate housing) prior to introduction to the
ultrafiltration system. Large volume subsurface water samples were collected
using successive casts of a rosette equipped with 24 x 12 L Niskin bottles.

Tangential-Flow Ultrafiltration
The main UF system was constructed using a modified design of the system
described in Roland et al. (2009), and expanded on by Walker et al. (2011).
Briefly, the system was comprised of four-spiral wound PES UF membranes,
having a nominal molecular weight cut off of 2.5 kD (GE Osmonics GH2540F30,
40-inch long, 2.5-inch diameter). The membranes were mounted in stainless
steel housings, plumbed in parallel to a 100 L fluorinated HDPE reservoir,
with flow driven by a 1.5 HP stainless steel centrifugal pump (Goulds Pumps,
Stainless steel centrifugal pump, NPE series 1 x 1-1/4 -6, close coupled to a
1-1/2 horsepower, 3500 RPM, 60 Hz, 3 phase, Open Drip Proof Motor; 5.75 Inch
Impeller Diameter, Standard Viton Mechanical Seals). All other system plumbing
components contacting seawater were composed of polytetrafluoroethylene (PTFE)
or stainless steel.

The system was run continuously at a membrane pressure of 40-50 psi, resulting
in permeation flow rates of 1-2 L/min, depending primarily on the temperature
of the feed seawater. Sample water was fed into the system using peristaltic
pumps and platinum cured silicone tubing at a flow rate matched to the system
permeation rates to ensure a constant system volume of approximately 100 L.

Seawater samples of 3000-4000 L were concentrated to a final retentate volume
of 15-20 L, drained from the system into acid washed PC carboys and
refrigerated (less than 12 hours at 2C) until the next phase of processing.
Samples requiring storage for longer than 12 hours were frozen and stored at
-20\u00b0C. The UF system was then reconfigured to a smaller volume system,
consisting of a single membrane having a smaller nominal molecular weight
cutoff (GE Osmonics GE2540F30, 40-inch long, 2.5-inch diameter, 1 kD MWCO),
and a 2.5 L PES reservoir for further volume reduction and subsequent salt
removal (diafiltration). Using this smaller system, samples were reduced to
2-3 L under lower pressure (25 psi, permeation rate = 250 mL/min). Samples
were then diafiltered using 40 L of 18.2 M\u03a9 Milli-Q (ultrapure) water,
adding water to the sample retentate reservoir at the same rate of membrane
permeation. Reduced and diafiltered samples were stored in acid washed PC
bottles at -20\u00b0C for transport. In the laboratory, samples were further
concentrated by rotary evaporation using pre-combusted glassware (450 \u00b0C,
5 h). A molecular sieve and a liquid nitrogen trap were placed between the
vacuum pump and rotovap chamber to ensure no contamination of isolated
material by back streaming of hydrocarbons or other contaminants. After
reduction to 50-100 mL, samples were dried to powder via centrifugal
evaporation in PTFE centrifuge tubes. Dry material was homogenized with an
ethanol cleaned agate mortar and pestle, transferred to pre-combusted glass
vials, and stored in a desiccation cabinet until subsequent analyses.

Solid Phase Extraction
Solid phase extraction was conducted using PPL sorbent (Agilent Bondesil
PPL, 125 \u00b5m particle size, part # 5982-0026) following the general
recommendations of Dittmar et al. (2008) and Green et al. (2014), including
loading rates, seawater to sorbent ratios, and elution volumes and rates.
Between 300 and 500 g of sorbent was used for each extraction, depending on
sample volume and DOC concentration, with average loading of 4.2 \u00b1 1.5 L
UF permeate per g sorbent representing 1.9 \u00b1 0.6 mg DOC per g sorbent or
a DOC to sorbent mass ratio of 1:600 \u00b1 200. This is in line with both the
recommendations of Dittmar et al. (2008) (maximum loading = 10 L seawater per
g sorbent) and Li et al. (2016) (DOC to sorbent ratio = 1:800). Permeate from
the UF system was fed through PTFE tubing to a pair of 200 L HDPE barrels. The
permeate water was then acidified in 200 L batches to pH 2 by adding 400 mL of
6 M HCl (Fisher Chemical, ACS Plus grade). Batch samples were mixed
continuously during collection, acidification, and loading using a peristaltic
pump and platinum cured Si and PTFE tubing positioned at the surface and
bottom of each barrel. Acidified batches of seawater permeate were then pumped
through the SPE sorbent. SPE flow rates were matched to UF permeation rates
(1-2 L/min), such that a pair of 200 L barrels allowed one barrel to be filled
while the contents of the other was passed through the sorbent.

Three custom SPE column configurations were used to contain the sorbent
material. The column configuration was modified several times for ease of use
on subsequent cruises. First, an open, gravity fed, large (49 mm ID x 1000 mm
length, 1875 mL volume) glass chromatography column with 40 \u00b5m fritted
disk and PTFE stopcock (Kimble-Chase, Kontes) was used. Next, we tested a
custom built high-pressure SS housing (10 cm ID x 3.5 cm bed height), and
finally a parallel combination of 2 medium-pressure glass chromatography
columns (Kimble-Chase, Kontes, Chromaflex LC, 4.8 mm ID x 30 cm, 543 mL
volume). While all designs proved to be functionally equivalent, the latter
parallel combination of 2 medium-pressure glass columns ultimately provided
the best configuration in order to maximize flow rates while simultaneously
optimizing the ratio of sorbent bed height to loading speed. Further, the
commercial availability and ease of use associated with this configuration
made it our preferred design.

Following sample loading, the SPE sorbent was desalted with 6 L of pH 2
ultrapure water at a low flow rate (250-300 mL/min). After desalting, the SPE
sorbent was transferred to a glass chromatography column (75 mm ID x 300 mm
length, 40 \u00b5m fritted disk, PTFE stopcock) with ultrapure water rinses to
ensure quantitative transfer. Isolated organic material was then eluted from
the sorbent with five to six 500 mL additions of methanol. The eluted methanol
solution was stored in pre-combusted amber glass bottles at -20\u00b0C for
transport. Similar to UF samples, the methanol-eluted solutions were first
reduced by rotary evaporation to 50-100 mL. Samples were then dried to powder
via centrifugal evaporation in PTFE centrifuge tubes. Dry material was
homogenized with an ethanol cleaned agate mortar and pestle, transferred to
pre-combusted glass vials, and stored in a desiccation cabinet until elemental
and isotopic analyses.

Amino Acid Enantiomeric Analysis
AA enantiomers were analyzed by gas chromatography-mass spectrometry (GC-MS;
Agilent 7890A + 5975B) using a chiral column (Altech Chirasi-L-Val, 50 m
length, 0.25 mm internal diameter, 0.16 \u03bcm film thickness). 1 \u03bcL of
sample was injected through a splitless inlet at 200\u00b0C, using helium
carrier (0.9 mL/min). Individual amino acids were separated using a 4-ramp,
57.5 min temperature program: 45\u00b0C start;\u00a0 2\u00b0C/min to
75\u00b0C;\u00a0 4\u00b0C/min to 110\u00b0C;\u00a0 1\u00b0C/min to
125\u00b0C;\u00a0 4\u00b0C/min to a final temperature of 200\u00b0C.
Quantification was based on retention times for authentic D and L standards of
each AA, coupled with ion peak areas obtained using single-ion monitoring,
based on the following characteristic ion fragments (m/z): Alanine (Ala), 140;
valine (Val), 168.1; threonine (Thr), 153; glycine (Gly), 126; isoleucine and
leucine (Ile and Leu), 182.1; serine (Ser), 138; proline (Pro), 166.1;
aspartic acid (Asp), 184; glutamic acid (Glu), 180; and phenylalanine (Phe),
190.1. Total amino acid yields, and relative abundance were quantified using
mixed L-AA standards in a linear four-point calibration curve ranging from
1-1000 \u03bcmol/AA. For each AA, peak areas for both enantiomers were
converted to molar quantities using the calibration curve for the
corresponding ion fragment. Molar percentage abundance (Mol%) for each AA
measured was calculated using the sum of the D and L enantiomers.
attribute NC_GLOBAL awards_0_award_nid String 701743
attribute NC_GLOBAL awards_0_award_number String OCE-1358041
attribute NC_GLOBAL awards_0_data_url String http://www.nsf.gov/awardsearch/showAward.do?AwardNumber=1358041 (external link)
attribute NC_GLOBAL awards_0_funder_name String NSF Division of Ocean Sciences
attribute NC_GLOBAL awards_0_funding_acronym String NSF OCE
attribute NC_GLOBAL awards_0_funding_source_nid String 355
attribute NC_GLOBAL awards_0_program_manager String Henrietta N Edmonds
attribute NC_GLOBAL awards_0_program_manager_nid String 51517
attribute NC_GLOBAL cdm_data_type String Other
attribute NC_GLOBAL comment String Amino Acid Enantiomeric Ratios (D/L)
PI: Matthew McCarthy (UC Santa Cruz)
Co-PI: Thomas Guilderson (UC Santa Cruz)
Version date: 13 May 2020
attribute NC_GLOBAL Conventions String COARDS, CF-1.6, ACDD-1.3
attribute NC_GLOBAL creator_email String info at bco-dmo.org
attribute NC_GLOBAL creator_name String BCO-DMO
attribute NC_GLOBAL creator_type String institution
attribute NC_GLOBAL creator_url String https://www.bco-dmo.org/ (external link)
attribute NC_GLOBAL data_source String extract_data_as_tsv version 2.3 19 Dec 2019
attribute NC_GLOBAL dataset_current_state String Final and no updates
attribute NC_GLOBAL date_created String 2020-05-13T19:42:12Z
attribute NC_GLOBAL date_modified String 2020-05-20T15:39:28Z
attribute NC_GLOBAL defaultDataQuery String &time<now
attribute NC_GLOBAL doi String 10.26008/1912/bco-dmo.811458.1
attribute NC_GLOBAL geospatial_vertical_max double 2500.0
attribute NC_GLOBAL geospatial_vertical_min double 7.5
attribute NC_GLOBAL geospatial_vertical_positive String down
attribute NC_GLOBAL geospatial_vertical_units String m
attribute NC_GLOBAL infoUrl String https://www.bco-dmo.org/dataset/811458 (external link)
attribute NC_GLOBAL institution String BCO-DMO
attribute NC_GLOBAL instruments_0_acronym String Niskin bottle
attribute NC_GLOBAL instruments_0_dataset_instrument_nid String 811469
attribute NC_GLOBAL instruments_0_description String A Niskin bottle (a next generation water sampler based on the Nansen bottle) is a cylindrical, non-metallic water collection device with stoppers at both ends. The bottles can be attached individually on a hydrowire or deployed in 12, 24, or 36 bottle Rosette systems mounted on a frame and combined with a CTD. Niskin bottles are used to collect discrete water samples for a range of measurements including pigments, nutrients, plankton, etc.
attribute NC_GLOBAL instruments_0_instrument_external_identifier String https://vocab.nerc.ac.uk/collection/L22/current/TOOL0412/ (external link)
attribute NC_GLOBAL instruments_0_instrument_name String Niskin bottle
attribute NC_GLOBAL instruments_0_instrument_nid String 413
attribute NC_GLOBAL instruments_0_supplied_name String rosette equipped with 24 x 12 L Niskin bottles
attribute NC_GLOBAL instruments_1_acronym String Pump-Ship Intake
attribute NC_GLOBAL instruments_1_dataset_instrument_nid String 811468
attribute NC_GLOBAL instruments_1_description String The 'Pump-underway ship intake' system indicates that samples are from the ship's clean water intake pump. This is essentially a surface water sample from a source of uncontaminated near-surface (commonly 3 to 7 m) seawater that can be pumped continuously to shipboard laboratories on research vessels. There is typically a temperature sensor near the intake (known as the hull temperature) to provide measurements that are as close as possible to the ambient water temperature. The flow from the supply is typically directed through continuously logged sensors such as a thermosalinograph and a fluorometer. Water samples are often collected from the underway supply that may also be referred to as the non-toxic supply. Ideally the data contributor has specified the depth in the ship's hull at which the pump is mounted.
attribute NC_GLOBAL instruments_1_instrument_external_identifier String https://vocab.nerc.ac.uk/collection/L05/current/31/ (external link)
attribute NC_GLOBAL instruments_1_instrument_name String Pump - Surface Underway Ship Intake
attribute NC_GLOBAL instruments_1_instrument_nid String 534
attribute NC_GLOBAL instruments_1_supplied_name String underway sampling system
attribute NC_GLOBAL instruments_2_acronym String Gas Chromatograph
attribute NC_GLOBAL instruments_2_dataset_instrument_nid String 811475
attribute NC_GLOBAL instruments_2_description String Instrument separating gases, volatile substances, or substances dissolved in a volatile solvent by transporting an inert gas through a column packed with a sorbent to a detector for assay. (from SeaDataNet, BODC)
attribute NC_GLOBAL instruments_2_instrument_external_identifier String https://vocab.nerc.ac.uk/collection/L05/current/LAB02/ (external link)
attribute NC_GLOBAL instruments_2_instrument_name String Gas Chromatograph
attribute NC_GLOBAL instruments_2_instrument_nid String 661
attribute NC_GLOBAL instruments_2_supplied_name String GC-MS; Agilent 7890A + 5975B
attribute NC_GLOBAL instruments_3_acronym String Mass Spec
attribute NC_GLOBAL instruments_3_dataset_instrument_nid String 811476
attribute NC_GLOBAL instruments_3_description String General term for instruments used to measure the mass-to-charge ratio of ions; generally used to find the composition of a sample by generating a mass spectrum representing the masses of sample components.
attribute NC_GLOBAL instruments_3_instrument_external_identifier String https://vocab.nerc.ac.uk/collection/L05/current/LAB16/ (external link)
attribute NC_GLOBAL instruments_3_instrument_name String Mass Spectrometer
attribute NC_GLOBAL instruments_3_instrument_nid String 685
attribute NC_GLOBAL instruments_3_supplied_name String GC-MS; Agilent 7890A + 5975B
attribute NC_GLOBAL keywords String acid, amino, amino_acid, bco, bco-dmo, biological, chemical, D_L_ratio, D_L_ratio_stdev, data, dataset, depth, deviation, dmo, erddap, management, mol, Mol_pcnt, Mol_pcnt_stdev, oceanography, office, pcnt, pcnt_D, pcnt_D_stdev, preliminary, ratio, sample, sample_type, season, standard, standard deviation, stdev, type, year
attribute NC_GLOBAL license String https://www.bco-dmo.org/dataset/811458/license (external link)
attribute NC_GLOBAL metadata_source String https://www.bco-dmo.org/api/dataset/811458 (external link)
attribute NC_GLOBAL param_mapping String {'811458': {'depth': 'flag - depth'}}
attribute NC_GLOBAL parameter_source String https://www.bco-dmo.org/mapserver/dataset/811458/parameters (external link)
attribute NC_GLOBAL people_0_affiliation String University of California-Santa Cruz
attribute NC_GLOBAL people_0_affiliation_acronym String UC Santa Cruz
attribute NC_GLOBAL people_0_person_name String Matthew D. McCarthy
attribute NC_GLOBAL people_0_person_nid String 557245
attribute NC_GLOBAL people_0_role String Principal Investigator
attribute NC_GLOBAL people_0_role_type String originator
attribute NC_GLOBAL people_1_affiliation String University of California-Santa Cruz
attribute NC_GLOBAL people_1_affiliation_acronym String UC Santa Cruz
attribute NC_GLOBAL people_1_person_name String Thomas Guilderson
attribute NC_GLOBAL people_1_person_nid String 51494
attribute NC_GLOBAL people_1_role String Co-Principal Investigator
attribute NC_GLOBAL people_1_role_type String originator
attribute NC_GLOBAL people_2_affiliation String Woods Hole Oceanographic Institution
attribute NC_GLOBAL people_2_affiliation_acronym String WHOI BCO-DMO
attribute NC_GLOBAL people_2_person_name String Shannon Rauch
attribute NC_GLOBAL people_2_person_nid String 51498
attribute NC_GLOBAL people_2_role String BCO-DMO Data Manager
attribute NC_GLOBAL people_2_role_type String related
attribute NC_GLOBAL project String DON Microbial Nitrogen Pump
attribute NC_GLOBAL projects_0_acronym String DON Microbial Nitrogen Pump
attribute NC_GLOBAL projects_0_description String Dissolved organic nitrogen is one of the most important - but perhaps least understood - components of the modern ocean nitrogen cycle. While dissolved organic nitrogen represents a main active reservoir of fixed and seemingly biologically-available nitrogen, at the same time most of ocean's dissolved organic nitrogen pool is also apparently unavailable for use by organisms. Recently, the idea of the "Microbial Carbon Pump" has emerged, providing a renewed focus on microbes as primary agents for the formation of biologically-available dissolved material. However, the role that microbes play in transformation of biologically-available dissolved organic nitrogen is still lacking. In order to fill gaps in this knowledge, researchers from the University of California Santa Cruz will apply a series of new analytical approaches to test the role of microbial source and transformation in formation of the ocean's biologically-available dissolved organic nitrogen pool. Results from this study will address one of the major unknowns of both chemical oceanography and the ocean nitrogen cycle.
Broader Impacts:
This proposal will provide oceanographers new tools to test ideas of microbial organic matter sequestration in a world where the oceans are rapidly changing. High school, undergraduate, graduate and post-doctoral education will be furthered through active participation in lab, field, and data synthesis activities.
attribute NC_GLOBAL projects_0_end_date String 2017-03
attribute NC_GLOBAL projects_0_geolocation String North Pacific Subtropical Gyre (HOT station), North Atlantic Subtropical Gyre (BATS time series station), California Margin
attribute NC_GLOBAL projects_0_name String The Microbial Nitrogen Pump: Coupling 14C and Compound-specific Amino Acids to Understand the Role of Microbial Transformations in the Refractory Ocean DON Pool
attribute NC_GLOBAL projects_0_project_nid String 701744
attribute NC_GLOBAL projects_0_start_date String 2014-04
attribute NC_GLOBAL publisher_name String Biological and Chemical Oceanographic Data Management Office (BCO-DMO)
attribute NC_GLOBAL publisher_type String institution
attribute NC_GLOBAL sourceUrl String (local files)
attribute NC_GLOBAL standard_name_vocabulary String CF Standard Name Table v55
attribute NC_GLOBAL subsetVariables String location
attribute NC_GLOBAL summary String Amino acid enantiomeric ratios (D/L) of high and low molecular weight (HMW,
LMW) DOM collected from the North Pacific Subtropical Gyre and Central North
Atlantic. These data were published in Broek et al. (2019) and Broek et al.
(2017).
attribute NC_GLOBAL title String Amino acid enantiomeric ratios (D/L) of high and low molecular weight (HMW, LMW) DOM collected from the North Pacific Subtropical Gyre and Central North Atlantic
attribute NC_GLOBAL version String 1
attribute NC_GLOBAL xml_source String osprey2erddap.update_xml() v1.5
variable location   String  
attribute location bcodmo_name String site
attribute location description String Sample collection location. HOT = Hawaii Ocean Time Series station ALOHA (22° 45'N, 158° 00'W) in North Pacific Subtropical Gyre (NPSG); BATS = Hawaii Ocean Time Series station ALOHA (22° 45'N, 158° 00'W) in North Pacific Subtropical Gyre (NPSG)
attribute location long_name String Location
attribute location units String unitless
variable year   short  
attribute year _FillValue short 32767
attribute year actual_range short 2014, 2015
attribute year bcodmo_name String year
attribute year description String Year of sample collection; format: YYYY
attribute year long_name String Year
attribute year nerc_identifier String https://vocab.nerc.ac.uk/collection/P01/current/YEARXXXX/ (external link)
attribute year units String unitless
variable season   String  
attribute season bcodmo_name String season
attribute season description String Season of sample collection
attribute season long_name String Season
attribute season units String unitless
variable sample_type   String  
attribute sample_type bcodmo_name String sample_type
attribute sample_type description String DOM Fraction
attribute sample_type long_name String Sample Type
attribute sample_type units String unitless
variable depth   double  
attribute depth _CoordinateAxisType String Height
attribute depth _CoordinateZisPositive String down
attribute depth _FillValue double NaN
attribute depth actual_range double 7.5, 2500.0
attribute depth axis String Z
attribute depth bcodmo_name String depth
attribute depth colorBarMaximum double 8000.0
attribute depth colorBarMinimum double -8000.0
attribute depth colorBarPalette String TopographyDepth
attribute depth description String Sample depth
attribute depth ioos_category String Location
attribute depth long_name String Depth
attribute depth nerc_identifier String https://vocab.nerc.ac.uk/collection/P09/current/DEPH/ (external link)
attribute depth positive String down
attribute depth standard_name String depth
attribute depth units String m
variable amino_acid   String  
attribute amino_acid bcodmo_name String amino_acid
attribute amino_acid description String Amino acid
attribute amino_acid long_name String Amino Acid
attribute amino_acid units String unitless
variable Mol_pcnt   float  
attribute Mol_pcnt _FillValue float NaN
attribute Mol_pcnt actual_range float 1.6, 38.6
attribute Mol_pcnt bcodmo_name String amino_conc
attribute Mol_pcnt description String Relative amino acid molar abundance
attribute Mol_pcnt long_name String Mol Pcnt
attribute Mol_pcnt units String unitless (percent)
variable Mol_pcnt_stdev   float  
attribute Mol_pcnt_stdev _FillValue float NaN
attribute Mol_pcnt_stdev actual_range float 0.2, 3.9
attribute Mol_pcnt_stdev bcodmo_name String amino_conc
attribute Mol_pcnt_stdev description String Standard deviation of Mol_pcnt
attribute Mol_pcnt_stdev long_name String Mol Pcnt Stdev
attribute Mol_pcnt_stdev units String unitless (percent)
variable pcnt_D   float  
attribute pcnt_D _FillValue float NaN
attribute pcnt_D actual_range float 1.3, 44.3
attribute pcnt_D bcodmo_name String amino_conc
attribute pcnt_D description String Relative amount of D-amino acid enantiomer
attribute pcnt_D long_name String PCNT D
attribute pcnt_D units String unitless (percent)
variable pcnt_D_stdev   float  
attribute pcnt_D_stdev _FillValue float NaN
attribute pcnt_D_stdev actual_range float 0.3, 1.4
attribute pcnt_D_stdev bcodmo_name String amino_conc
attribute pcnt_D_stdev description String Standard deviation of pcnt_D
attribute pcnt_D_stdev long_name String Pcnt D Stdev
attribute pcnt_D_stdev units String unitless (percent)
variable D_L_ratio   float  
attribute D_L_ratio _FillValue float NaN
attribute D_L_ratio actual_range float 0.01, 0.79
attribute D_L_ratio bcodmo_name String amino_conc
attribute D_L_ratio description String Ratio of D-AA to L-AA abundance
attribute D_L_ratio long_name String D L Ratio
attribute D_L_ratio units String unitless
variable D_L_ratio_stdev   float  
attribute D_L_ratio_stdev _FillValue float NaN
attribute D_L_ratio_stdev actual_range float 0.003, 0.014
attribute D_L_ratio_stdev bcodmo_name String amino_conc
attribute D_L_ratio_stdev description String Standard deviation of D_L_ratio
attribute D_L_ratio_stdev long_name String D L Ratio Stdev
attribute D_L_ratio_stdev units String unitless

The information in the table above is also available in other file formats (.csv, .htmlTable, .itx, .json, .jsonlCSV1, .jsonlCSV, .jsonlKVP, .mat, .nc, .nccsv, .tsv, .xhtml) via a RESTful web service.


 
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