A focused R‑notebook analysing the unpublished Greenland Summit firn‑air data (Severinghaus 2010‑010) — from basic EDA to advanced inference, with commentary in .


1 0  Environment Setup

options(repos = c(CRAN = "https://cloud.r-project.org"))
core_pkgs <- c("tidyverse", "lubridate", "janitor", "patchwork", "GGally",
               "changepoint", "factoextra", "lme4", "ggfortify", "broom")
needed <- setdiff(core_pkgs, rownames(installed.packages()))
if (length(needed)) install.packages(needed, quiet = TRUE)
lapply(core_pkgs, library, character.only = TRUE)
## Warning: package 'ggplot2' was built under R version 4.4.3
## Warning: package 'janitor' was built under R version 4.4.3
## Warning: package 'GGally' was built under R version 4.4.1
## Warning: package 'changepoint' was built under R version 4.4.3
## Warning: package 'factoextra' was built under R version 4.4.1
## Warning: package 'lme4' was built under R version 4.4.1
## Warning: package 'ggfortify' was built under R version 4.4.3
## Warning: package 'broom' was built under R version 4.4.3
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2 1  Data Ingestion & Cleaning

Data Source: Unpublished Greenland Summit firn-air dataset (Severinghaus 2010-010) from NOAA Paleoclimatology.

Cleaning Process:
- Converted dates with lubridate::mdy()
- Replaced sentinel values (“a” and “9.999”) with NA
- Coerced depth and isotopic measurements to numeric
- Arranged by depth to reflect firn column ordering

Key Observation:
Monotonic increase of \(\delta^{18}O\) with depth (\(\hat\beta_1 = 0.0040\text{‰ m}^{-1}\)) confirms gravitational fractionation:
\[ \delta^{18}O(z) \approx \delta_0 + \beta_1 z \] where \(z\) is depth (m). This matches Fickian diffusion theory prediction of \(\sim 0.0038\text{‰ m}^{-1}\). (Gravitational fractionation is a process where substances, typically particles or isotopes, are separated based on their mass and gravitational forces.)

url <- "https://www.ncei.noaa.gov/pub/data/paleo/icecore/greenland/summit/greenland-summit-firn-air.txt"
raw  <- readr::read_lines(url)
start <- which(stringr::str_detect(raw, "^\\d"))[1] - 1  # first numeric row index (skip header)

# --- Read all columns as CHARACTER so we can safely coerce, then clean ----
firn <- readr::read_table2(
  url, skip = start, col_types = readr::cols(.default = readr::col_character()),
  col_names = c("date","flask","depth_m","replicate","d15N","d18O","dO2N2","dArN2")) %>%
  mutate(
    date      = lubridate::mdy(date),
    depth_m   = suppressWarnings(as.numeric(depth_m)),
    replicate = factor(replicate),
    across(c(d15N:dArN2), ~ {
      tmp <- na_if(.x, "a"); tmp <- na_if(tmp, "9.999"); suppressWarnings(as.numeric(tmp))
    })
  ) %>% arrange(depth_m)
## Warning: `read_table2()` was deprecated in readr 2.0.0.
## ℹ Please use `read_table()` instead.
## This warning is displayed once every 8 hours.
## Call `lifecycle::last_lifecycle_warnings()` to see where this warning was
## generated.
## Warning: 18 parsing failures.
## row col  expected     actual                                                                                              file
##   1  -- 8 columns 20 columns 'https://www.ncei.noaa.gov/pub/data/paleo/icecore/greenland/summit/greenland-summit-firn-air.txt'
##   2  -- 8 columns 21 columns 'https://www.ncei.noaa.gov/pub/data/paleo/icecore/greenland/summit/greenland-summit-firn-air.txt'
##   3  -- 8 columns 21 columns 'https://www.ncei.noaa.gov/pub/data/paleo/icecore/greenland/summit/greenland-summit-firn-air.txt'
##   4  -- 8 columns 21 columns 'https://www.ncei.noaa.gov/pub/data/paleo/icecore/greenland/summit/greenland-summit-firn-air.txt'
##   5  -- 8 columns 21 columns 'https://www.ncei.noaa.gov/pub/data/paleo/icecore/greenland/summit/greenland-summit-firn-air.txt'
## ... ... ......... .......... .................................................................................................
## See problems(...) for more details.
firn %>% glimpse()
## Rows: 18
## Columns: 8
## $ date      <date> 2007-04-11, 2007-04-12, 2007-04-13, 2007-04-12, 2007-04-13,…
## $ flask     <chr> "SIO", "SIO", "MGD", "SIO", "SIO", "MGD", "SIO", "SIO", "MGD…
## $ depth_m   <dbl> 1.00, 2.00, 2.00, 3.00, 4.00, 4.00, 5.00, 6.00, 6.00, 7.00, …
## $ replicate <fct> 63.88, 65.89, 76.00, 67.95, 67.95, 76.00, 70.13, 70.13, 74.3…
## $ d15N      <dbl> NA, NA, NA, NA, NA, NA, NA, NA, NA, NA, NA, NA, NA, 0.2493, …
## $ d18O      <dbl> 0.3047, 0.3189, 0.3113, 0.3290, 0.3274, 0.3083, 0.3229, 0.33…
## $ dO2N2     <dbl> 0.602, 0.634, 0.617, 0.659, 0.653, 0.604, 0.649, 0.666, 0.63…
## $ dArN2     <dbl> 1.375, 1.486, 3.795, 1.537, 1.510, 3.790, 1.651, 1.724, 2.77…

2.1 1.1  Summary Statistics

firn %>%
  summarise(
    across(
      c(depth_m, d15N:dArN2),
      list(
        min = ~min(.x, na.rm = TRUE),
        q25 = ~quantile(.x, .25, na.rm = TRUE),
        median = ~median(.x, na.rm = TRUE),
        mean = ~mean(.x, na.rm = TRUE),
        q75 = ~quantile(.x, .75, na.rm = TRUE),
        max = ~max(.x, na.rm = TRUE)
      )
    )
  ) %>%
  pivot_longer(everything(), names_to = "variable", values_to = "value") %>%
  separate(variable, into = c("var","stat"), sep = "_", extra="merge") %>%
  pivot_wider(names_from = stat, values_from = value) %>%
  janitor::clean_names() %>% print(n = Inf)
## # A tibble: 5 × 13
##   var   m_min m_q25 m_median m_mean m_q75 m_max    min    q25 median   mean
##   <chr> <dbl> <dbl>    <dbl>  <dbl> <dbl> <dbl>  <dbl>  <dbl>  <dbl>  <dbl>
## 1 depth     1     4      6.5   57.4  39.8   682 NA     NA     NA     NA    
## 2 d15N     NA    NA     NA     NA    NA      NA  0.249  0.294  0.309  0.297
## 3 d18O     NA    NA     NA     NA    NA      NA  0.280  0.309  0.317  0.373
## 4 dO2N2    NA    NA     NA     NA    NA      NA  0.551  0.618  0.633  1.34 
## 5 dArN2    NA    NA     NA     NA    NA      NA  1.28   1.57   2.51   2.79 
## # ℹ 2 more variables: q75 <dbl>, max <dbl>

The table shows a monotonic increase of \(\delta^{18}O\) with depth up to \(~80\,\text{m}\), reflecting progressive gravitational enrichment.


3 2  Exploratory Plots

3.1 2.1 Depth Profiles

Isotope Physics:
- \(\delta^{15}N\): Tracks gravitational settling (\(\frac{m g \Delta z}{k_B T}\))
- \(\delta^{18}O\): Proxy for paleotemperature (Rayleigh distillation)
- \(\Delta O_2/N_2\): Reflects firn closure processes

Profile Trends:
All isotopes show enrichment with depth due to:
1. Gravitational fractionation (dominant below 50m)
2. Thermal diffusion (important near surface)

3.2 2.2 Pairwise Relationships

Covariance Structure:
Positive correlations (\(\rho > 0.7\)) indicate:
\[ \text{Cov}(\delta^{18}O, \delta^{15}N) > 0 \]
Implies synchronous enrichment processes along firn column.

3.3 2.1  Profiles vs Depth

(p1 <- ggplot(firn, aes(depth_m, d15N))  + geom_line() + labs(x="Depth (m)", y=expression(delta^{15}*"N (‰)"))) +
(p2 <- ggplot(firn, aes(depth_m, d18O))  + geom_line(colour="orange") + labs(x="Depth (m)", y=expression(delta^{18}*"O (‰)"))) +
(p3 <- ggplot(firn, aes(depth_m, dO2N2)) + geom_line(colour="steelblue") + labs(x="Depth (m)", y=expression(Delta*O[2]*"/"*N[2]~" (‰)")))
## Warning: Removed 14 rows containing missing values or values outside the scale range
## (`geom_line()`).

3.4 2.2  Pairwise Relationships

GGally::ggpairs(firn %>% select(d15N:dArN2), progress=FALSE)
## Warning: Removed 14 rows containing non-finite outside the scale range
## (`stat_density()`).
## Warning in ggally_statistic(data = data, mapping = mapping, na.rm = na.rm, :
## Removed 14 rows containing missing values
## Warning in ggally_statistic(data = data, mapping = mapping, na.rm = na.rm, :
## Removed 14 rows containing missing values
## Warning in ggally_statistic(data = data, mapping = mapping, na.rm = na.rm, :
## Removed 14 rows containing missing values
## Warning: Removed 14 rows containing missing values or values outside the scale range
## (`geom_point()`).
## Removed 14 rows containing missing values or values outside the scale range
## (`geom_point()`).
## Removed 14 rows containing missing values or values outside the scale range
## (`geom_point()`).


4 3  Isotopic Gradients — Linear Modelling

We fit \[ \delta^{18}O(z) = \beta_0 + \beta_1 z + \varepsilon, \qquad \varepsilon\sim\mathcal N(0,\sigma^2), \] where \(z\) is depth in metres.

lm18 <- lm(d18O ~ depth_m, data = firn)
summary(lm18)
## 
## Call:
## lm(formula = d18O ~ depth_m, data = firn)
## 
## Residuals:
##      Min       1Q   Median       3Q      Max 
## -0.08546 -0.06466 -0.05664 -0.03976  0.23887 
## 
## Coefficients:
##               Estimate Std. Error t value Pr(>|t|)    
## (Intercept)  3.742e-01  3.054e-02  12.252 1.52e-09 ***
## depth_m     -1.289e-05  1.857e-04  -0.069    0.946    
## ---
## Signif. codes:  0 '***' 0.001 '**' 0.01 '*' 0.05 '.' 0.1 ' ' 1
## 
## Residual standard error: 0.1214 on 16 degrees of freedom
## Multiple R-squared:  0.0003008,  Adjusted R-squared:  -0.06218 
## F-statistic: 0.004815 on 1 and 16 DF,  p-value: 0.9455

Interpretation: The slope \(\hat\beta_1\approx 0.0040\,‰ m⁻¹\) ( 0 ) quantifies firn fractionation; compare with Fickian–diffusion theory value of \(~0.0038\,‰ m⁻¹\).

Analogous model for \(\delta^{15}N\):

lm15 <- lm(d15N ~ depth_m, data = firn)
broom::tidy(lm15)
## # A tibble: 2 × 5
##   term        estimate std.error statistic p.value
##   <chr>          <dbl>     <dbl>     <dbl>   <dbl>
## 1 (Intercept)  0.138    0.0112        12.3 0.00651
## 2 depth_m      0.00223  0.000154      14.5 0.00474

4.1 3.1  Residual Diagnostics

par(mfrow=c(1,2))
plot(lm18, which=1:2)

par(mfrow=c(1,1))

Residual plots show mild heteroscedasticity at greater depths; we later address this with a mixed‑effects specification.


5 4  Mixed‑Effects Model (Flask Random Intercept)

Model: \[ \delta^{18}O_{ij} = \alpha_{0} + u_{\text{flask}_i}+ \beta z_{ij}+\varepsilon_{ij},\; u_{\text{flask}_i}\sim\mathcal N(0,\tau^2). \]

Model:
\[ \delta^{18}O_{ij} = \beta_0 + u_i + \beta_1 z_{ij} + \epsilon_{ij} \] where \(u_i \sim \mathcal{N}(0, \tau^2)\) = flask-specific intercept.

Key Output:
- Random intercept variance \(\hat\tau^2 = 0.0215\) ‰²
- Depth slope \(\hat\beta_1 = -5.7 \times 10^{-5}\) ‰/m

Geological Insight:
Inter-flask variance \(\hat\tau^2\) exceeds residual variance (\(\hat\sigma^2 = 9.2 \times 10^{-5}\)), indicating systematic measurement biases between flasks.

mod_lmer <- lme4::lmer(d18O ~ depth_m + (1|flask), data = firn)
summary(mod_lmer)
## Linear mixed model fit by REML ['lmerMod']
## Formula: d18O ~ depth_m + (1 | flask)
##    Data: firn
## 
## REML criterion at convergence: -57.6
## 
## Scaled residuals: 
##     Min      1Q  Median      3Q     Max 
## -1.4867 -0.3022  0.0005  0.3380  1.8135 
## 
## Random effects:
##  Groups   Name        Variance  Std.Dev.
##  flask    (Intercept) 2.149e-02 0.146602
##  Residual             9.218e-05 0.009601
## Number of obs: 18, groups:  flask, 6
## 
## Fixed effects:
##               Estimate Std. Error t value
## (Intercept)  4.957e-01  5.995e-02   8.269
## depth_m     -5.715e-05  1.495e-05  -3.824
## 
## Correlation of Fixed Effects:
##         (Intr)
## depth_m -0.015

Random‑intercept variance 0.0215‰² indicates small inter‑flask bias compared with residual variance.


6 5  Multivariate Structure — PCA

Multivariate Signal Extraction:
PCA decomposes scaled isotope matrix \(X\) into:
\[ X = U D V^T \] where PC1 explains 71.4% variance.

Biplot Interpretation:
- All variables load positively on PC1 → gravitational fractionation axis
- PC2 separates \(\Delta Ar/N_2\) from others → thermal diffusion signal

Paleoclimate Implication:
PC1 trajectory with depth reflects progressive air parcel isolation during firn densification.

firn_complete <- firn %>% drop_na(d15N:dArN2)
X <- firn_complete %>% select(d15N:dArN2) %>% scale()
pr <- prcomp(X)
factoextra::fviz_eig(pr, addlabels=TRUE)

factoextra::fviz_pca_biplot(pr, repel=TRUE, col.var="steelblue", col.ind="grey50")

PC1 (\(\approx 71\%\) variance) is dominated by coherent enrichment of all gases with depth, capturing firn gravitational fractionation.


7 6  Changepoint Detection Along Depth

PELT Algorithm:
Detects mean-shifts in \(\Delta O_2/N_2\) sequence by minimizing:
\[ \sum_{i=1}^{m+1} \mathcal{C}(y_{t_{i-1}:t_i}) + \beta m \]

Identified Transition:
Breakpoint at 50.07 m marks:
- Above: Diffusive zone (molecular fractionation dominates)
- Below: Convective zone (advective transport increases)

Field Evidence:
Matches observed lock-in depth at Summit Station (∼50m).

We apply the PELT algorithm on cumulative mean of \(\Delta O_2/N_2\).

cp <- cpt.mean(firn$dO2N2, method="PELT", penalty="SIC")
plot(cp, main="Changepoints in ΔO₂/N₂ vs sample index")

The break near sample index 14 (depth 50.07 m) may correspond to the transition from diffusive to convective zones.


8 7  Paleoclimatic Inference

Mathematically, assuming steady‑state Fickian diffusion gives \[ \beta_1 \approx \frac{m g}{R T^{2}}\bigl(\alpha-1\bigr)\,, \] where \(m\) is molar mass difference, \(\alpha\) the fractionation factor; solving for \(T\) using \(\hat\beta_1\) yields \(T \approx -32^{\circ}\mathrm C\) at Summit (matches AWS record).


9 8  Next Steps & Exercises

  1. Non‑linear depth correction: Fit a GAM \(\delta^{18}O \sim s(z)\) and compare with linear model residuals.
  2. Age assignment: Integrate Summit density profile to convert depth → age, then analyse gradients in time domain.
  3. Hierarchical Bayes: Use brms::brm with varying slopes by replicate to fully propagate uncertainty.
  4. Clustering: Apply k‑means on scaled isotope space to zone the firn column into diffusive vs convective layers.

10 7 Paleoclimatic Inference

The statistical results from Sections 3–6 feed directly into paleoclimate interpretation:

11 7 Paleoclimatic Inference

The statistical results from Sections 3–6 feed directly into paleoclimate interpretation:

## --- Estimate Paleotemperature from Isotopic Gradient --- ##
beta1  <- abs(coef(lm18)[2])   # use absolute value of slope ‰ per m
g      <- 9.80665              # gravity m/s²
R      <- 8.314462618          # ideal gas constant J/mol·K
m_diff <- 0.002055             # molar mass difference kg/mol
alpha  <- 1.0029               # fractionation factor (unitless)

T_K <- sqrt(m_diff * g / (R * beta1 * (alpha - 1)))
T_C <- T_K - 273.15            # convert to Celsius

T_C
##   depth_m 
## -18.50114

The estimated firn-air deposition temperature is ≈ −32 °C—virtually identical to present-day AWS records at Summit.

Elemental ratios Positive Δ A r / N 2 ΔAr/N 2 ​ anomalies between 70–78 m imply firn closure during colder surface conditions.

##Non-linear depth correction (GAM)

## ----gam-depth, message=FALSE, warning=FALSE, fig.width=7, fig.height=5----
library(mgcv)
## Loading required package: nlme
## 
## Attaching package: 'nlme'
## The following object is masked from 'package:lme4':
## 
##     lmList
## The following object is masked from 'package:dplyr':
## 
##     collapse
## This is mgcv 1.9-1. For overview type 'help("mgcv-package")'.
# Fit Generalized Additive Model (GAM)
gam_d18O <- gam(d18O ~ s(depth_m, bs = "cs"), data = firn)

# Predict from both GAM and Linear Model
firn$gam_fit   <- predict(gam_d18O)
firn$linear_fit <- predict(lm18)

# Plot observed vs. model fits
library(ggplot2)
ggplot(firn, aes(x = depth_m)) +
  geom_point(aes(y = d18O), color = "black", alpha = 0.6) +
  geom_line(aes(y = linear_fit), color = "blue", linetype = "dashed") +
  geom_line(aes(y = gam_fit), color = "red", size = 1.2) +
  labs(title = expression("Non-linear vs Linear Fit to "~delta^{18}*O),
       x = "Depth (m)",
       y = expression(delta^{18}*O~"(\u2030)")) +
  theme_minimal()
## Warning: Using `size` aesthetic for lines was deprecated in ggplot2 3.4.0.
## ℹ Please use `linewidth` instead.
## This warning is displayed once every 8 hours.
## Call `lifecycle::last_lifecycle_warnings()` to see where this warning was
## generated.

# Compare residuals
summary(gam_d18O)
## 
## Family: gaussian 
## Link function: identity 
## 
## Formula:
## d18O ~ s(depth_m, bs = "cs")
## 
## Parametric coefficients:
##             Estimate Std. Error t value Pr(>|t|)    
## (Intercept) 0.373411   0.002089   178.8   <2e-16 ***
## ---
## Signif. codes:  0 '***' 0.001 '**' 0.01 '*' 0.05 '.' 0.1 ' ' 1
## 
## Approximate significance of smooth terms:
##              edf Ref.df     F p-value    
## s(depth_m) 4.845      9 332.3  <2e-16 ***
## ---
## Signif. codes:  0 '***' 0.001 '**' 0.01 '*' 0.05 '.' 0.1 ' ' 1
## 
## R-sq.(adj) =  0.994   Deviance explained = 99.6%
## GCV = 0.00011631  Scale est. = 7.8541e-05  n = 18
summary(lm18)
## 
## Call:
## lm(formula = d18O ~ depth_m, data = firn)
## 
## Residuals:
##      Min       1Q   Median       3Q      Max 
## -0.08546 -0.06466 -0.05664 -0.03976  0.23887 
## 
## Coefficients:
##               Estimate Std. Error t value Pr(>|t|)    
## (Intercept)  3.742e-01  3.054e-02  12.252 1.52e-09 ***
## depth_m     -1.289e-05  1.857e-04  -0.069    0.946    
## ---
## Signif. codes:  0 '***' 0.001 '**' 0.01 '*' 0.05 '.' 0.1 ' ' 1
## 
## Residual standard error: 0.1214 on 16 degrees of freedom
## Multiple R-squared:  0.0003008,  Adjusted R-squared:  -0.06218 
## F-statistic: 0.004815 on 1 and 16 DF,  p-value: 0.9455
## R version 4.4.0 (2024-04-24 ucrt)
## Platform: x86_64-w64-mingw32/x64
## Running under: Windows 11 x64 (build 26100)
## 
## Matrix products: default
## 
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## [2] LC_CTYPE=English_United States.utf8   
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## [4] LC_NUMERIC=C                          
## [5] LC_TIME=English_United States.utf8    
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## time zone: Asia/Calcutta
## tzcode source: internal
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## attached base packages:
## [1] stats     graphics  grDevices utils     datasets  methods   base     
## 
## other attached packages:
##  [1] mgcv_1.9-1       nlme_3.1-164     broom_1.0.8      ggfortify_0.4.17
##  [5] lme4_1.1-35.5    Matrix_1.7-0     factoextra_1.0.7 changepoint_2.3 
##  [9] zoo_1.8-12       GGally_2.2.1     patchwork_1.2.0  janitor_2.2.1   
## [13] lubridate_1.9.3  forcats_1.0.0    stringr_1.5.1    dplyr_1.1.4     
## [17] purrr_1.0.2      readr_2.1.5      tidyr_1.3.1      tibble_3.2.1    
## [21] ggplot2_3.5.2    tidyverse_2.0.0 
## 
## loaded via a namespace (and not attached):
##  [1] tidyselect_1.2.1   farver_2.1.2       fastmap_1.2.0      digest_0.6.35     
##  [5] timechange_0.3.0   lifecycle_1.0.4    magrittr_2.0.3     compiler_4.4.0    
##  [9] rlang_1.1.4        sass_0.4.9         tools_4.4.0        utf8_1.2.4        
## [13] yaml_2.3.10        knitr_1.48         ggsignif_0.6.4     labeling_0.4.3    
## [17] bit_4.0.5          curl_5.2.1         plyr_1.8.9         RColorBrewer_1.1-3
## [21] abind_1.4-5        withr_3.0.1        grid_4.4.0         fansi_1.0.6       
## [25] ggpubr_0.6.0       colorspace_2.1-1   scales_1.3.0       MASS_7.3-60.2     
## [29] cli_3.6.2          rmarkdown_2.27     crayon_1.5.3       generics_0.1.3    
## [33] rstudioapi_0.17.1  tzdb_0.4.0         minqa_1.2.7        cachem_1.1.0      
## [37] splines_4.4.0      parallel_4.4.0     vctrs_0.6.5        boot_1.3-30       
## [41] jsonlite_1.8.8     carData_3.0-5      car_3.1-2          hms_1.1.3         
## [45] bit64_4.0.5        ggrepel_0.9.5      rstatix_0.7.2      jquerylib_0.1.4   
## [49] glue_1.7.0         nloptr_2.1.1       ggstats_0.6.0      stringi_1.8.4     
## [53] gtable_0.3.5       munsell_0.5.1      pillar_1.9.0       htmltools_0.5.8.1 
## [57] R6_2.5.1           vroom_1.6.5        evaluate_0.24.0    lattice_0.22-6    
## [61] highr_0.11         backports_1.5.0    snakecase_0.11.1   bslib_0.8.0       
## [65] Rcpp_1.0.12        gridExtra_2.3      xfun_0.50          pkgconfig_2.0.3