From c1144753adfa0809003085009ebd85f8af9beda8 Mon Sep 17 00:00:00 2001 From: jranke Date: Tue, 10 Apr 2012 21:50:22 +0000 Subject: - Fitting and summaries now work with the new parameter transformations. - The SFORB models with metabolites is broken (see TODO) - Moved the vignette to the location recommended since R 2.14 - Added the missing documentation - Commented out the schaefer_complex_case test, as this version of mkin is not able to fit a model without sink and therefore mkin estimated parameters are quite different git-svn-id: svn+ssh://svn.r-forge.r-project.org/svnroot/kinfit/pkg/mkin@22 edb9625f-4e0d-4859-8d74-9fd3b1da38cb --- DESCRIPTION | 2 +- NAMESPACE | 1 + R/mkinfit.R | 69 +- R/mkinpredict.R | 90 + R/predict.mkinmod.R | 89 - R/transform_odeparms.R | 70 +- TODO | 9 +- inst/doc/Rplots.pdf | 23902 --------------------------------------- inst/doc/header.tex | 31 - inst/doc/mkin.Rnw | 162 - inst/doc/mkin.pdf | Bin 178902 -> 0 bytes inst/doc/references.bib | 62 - inst/doc/run.bat | 5 - inst/unitTests/runit.mkinfit.R | 56 +- inst/unitTests/runit.mkinmod.R | 74 +- man/ilr.Rd | 8 +- man/mkinpredict.Rd | 63 + man/summary.mkinfit.Rd | 11 +- man/transform_odeparms.Rd | 51 + vignettes/Rplots.pdf | 23902 +++++++++++++++++++++++++++++++++++++++ vignettes/header.tex | 31 + vignettes/mkin.Rnw | 164 + vignettes/mkin.pdf | Bin 0 -> 178902 bytes vignettes/references.bib | 62 + vignettes/run.bat | 5 + 25 files changed, 24507 insertions(+), 24412 deletions(-) create mode 100644 NAMESPACE create mode 100644 R/mkinpredict.R delete mode 100644 R/predict.mkinmod.R delete mode 100644 inst/doc/Rplots.pdf delete mode 100644 inst/doc/header.tex delete mode 100644 inst/doc/mkin.Rnw delete mode 100644 inst/doc/mkin.pdf delete mode 100644 inst/doc/references.bib delete mode 100644 inst/doc/run.bat create mode 100644 man/mkinpredict.Rd create mode 100644 man/transform_odeparms.Rd create mode 100644 vignettes/Rplots.pdf create mode 100644 vignettes/header.tex create mode 100644 vignettes/mkin.Rnw create mode 100644 vignettes/mkin.pdf create mode 100644 vignettes/references.bib create mode 100644 vignettes/run.bat diff --git a/DESCRIPTION b/DESCRIPTION index 6951ede..a7f33e2 100644 --- a/DESCRIPTION +++ b/DESCRIPTION @@ -3,7 +3,7 @@ Type: Package Title: Routines for fitting kinetic models with one or more state variables to chemical degradation data Version: 0.9-01 -Date: 2012-03-26 +Date: 2012-04-10 Author: Johannes Ranke, Katrin Lindenberger, René Lehmann Maintainer: Johannes Ranke Description: Calculation routines based on the FOCUS Kinetics Report (2006). diff --git a/NAMESPACE b/NAMESPACE new file mode 100644 index 0000000..06c6464 --- /dev/null +++ b/NAMESPACE @@ -0,0 +1 @@ +export(mkinmod, mkinpredict, mkinfit, mkinplot, mkin_long_to_wide, mkin_wide_to_long, ilr, invilr, transform_odeparms, backtransform_odeparms) diff --git a/R/mkinfit.R b/R/mkinfit.R index 47c39cf..44eb5b2 100644 --- a/R/mkinfit.R +++ b/R/mkinfit.R @@ -57,15 +57,17 @@ mkinfit <- function(mkinmod, observed, if (parmname == "tb") parms.ini[parmname] = 5 if (parmname == "g") parms.ini[parmname] = 0.5 } - parms.ini <- transform_odeparms(parms.ini, mod_vars) - + # Name the inital state variable values if they are not named yet if(is.null(names(state.ini))) names(state.ini) <- mod_vars + # Transform initial parameter values for fitting + transparms.ini <- transform_odeparms(parms.ini, mod_vars) + # Parameters to be optimised: # Kinetic parameters in parms.ini whose names are not in fixed_parms - parms.fixed <- parms.ini[fixed_parms] - parms.optim <- parms.ini[setdiff(names(parms.ini), fixed_parms)] + parms.fixed <- transparms.ini[fixed_parms] + parms.optim <- transparms.ini[setdiff(names(transparms.ini), fixed_parms)] # Inital state variables in state.ini whose names are not in fixed_initials state.ini.fixed <- state.ini[fixed_initials] @@ -83,8 +85,11 @@ mkinfit <- function(mkinmod, observed, if (length(mkinmod$map) == 1) { solution = "analytical" } else { - if (is.matrix(mkinmod$coefmat) & eigen) solution = "eigen" - else solution = "deSolve" + if (is.matrix(mkinmod$coefmat) && eigen) { + solution = "eigen" + } else { + solution = "deSolve" + } } cost.old <- 1e100 # The first model cost should be smaller than this value @@ -105,10 +110,10 @@ mkinfit <- function(mkinmod, observed, odeparms <- c(P[(length(state.ini.optim) + 1):length(P)], parms.fixed) - transparms <- transform_odeparms(odeparms, mod_vars) + parms <- backtransform_odeparms(odeparms, mod_vars) # Solve the system with current transformed parameter values - out <- predict(mkinmod, transparms, odeini, outtimes, solution_type = solution) + out <- mkinpredict(mkinmod, parms, odeini, outtimes, solution_type = solution, ...) assign("out_predicted", out, inherits=TRUE) @@ -123,8 +128,8 @@ mkinfit <- function(mkinmod, observed, if(plot) { outtimes_plot = seq(min(observed$time), max(observed$time), length.out=100) - out_plot <- predict(mkinmod, transparms, odeini, outtimes_plot, - solution_type = solution) + out_plot <- mkinpredict(mkinmod, parms, odeini, outtimes_plot, + solution_type = solution, ...) plot(0, type="n", xlim = range(observed$time), ylim = range(observed$value, na.rm=TRUE), @@ -160,8 +165,10 @@ mkinfit <- function(mkinmod, observed, fit$predicted <- out_predicted # Collect initial parameter values in two dataframes - fit$start <- data.frame(initial = c(state.ini.optim, parms.optim)) + fit$start <- data.frame(initial = c(state.ini.optim, + backtransform_odeparms(parms.optim, mod_vars))) fit$start$type = c(rep("state", length(state.ini.optim)), rep("deparm", length(parms.optim))) + fit$start$transformed = c(state.ini.optim, parms.optim) fit$fixed <- data.frame( value = c(state.ini.fixed, parms.fixed)) @@ -194,7 +201,7 @@ mkinfit <- function(mkinmod, observed, fit$errmin <- errmin # Calculate dissipation times DT50 and DT90 from parameters - parms.all = transform_odeparms(c(fit$par, parms.fixed), mod_vars) + parms.all = backtransform_odeparms(c(fit$par, parms.fixed), mod_vars) fit$distimes <- data.frame(DT50 = rep(NA, length(obs_vars)), DT90 = rep(NA, length(obs_vars)), row.names = obs_vars) fit$SFORB <- vector() @@ -285,16 +292,14 @@ mkinfit <- function(mkinmod, observed, data$variable <- ordered(data$variable, levels = obs_vars) fit$data <- data[order(data$variable, data$time), ] fit$atol <- atol + fit$parms.all <- parms.all class(fit) <- c("mkinfit", "modFit") return(fit) } -summary.mkinfit <- function(object, data = TRUE, distimes = TRUE, ff = TRUE, ...) { +summary.mkinfit <- function(object, data = TRUE, distimes = TRUE, ...) { param <- object$par - if (object$logk) { - names(param) <- sub("^k_", "log k_", names(param)) - } pnames <- names(param) p <- length(param) covar <- try(solve(0.5*object$hessian), silent = TRUE) # unscaled covariance @@ -304,7 +309,7 @@ summary.mkinfit <- function(object, data = TRUE, distimes = TRUE, ff = TRUE, ... covar <- matrix(data = NA, nrow = p, ncol = p) } else message <- "ok" - rownames(covar) <- colnames(covar) <-pnames + rownames(covar) <- colnames(covar) <- pnames rdf <- object$df.residual resvar <- object$ssr / rdf se <- sqrt(diag(covar) * resvar) @@ -312,12 +317,6 @@ summary.mkinfit <- function(object, data = TRUE, distimes = TRUE, ff = TRUE, ... tval <- param / se modVariance <- object$ssr / length(object$residuals) - if (!all(object$start$lower >=0)) { - message <- "Note that the one-sided t-test may not be appropriate if - parameter values below zero are possible." - warning(message) - } else message <- "ok" - param <- cbind(param, se) dimnames(param) <- list(pnames, c("Estimate", "Std. Error")) @@ -335,20 +334,17 @@ summary.mkinfit <- function(object, data = TRUE, distimes = TRUE, ff = TRUE, ... if(data) ans$data <- object$data ans$start <- object$start - # Fix names of parameters to show that they were transformed - names(ans$start) <- sub("^k_", "log k_", names(ans$start)) - ans$fixed <- object$fixed ans$errmin <- object$errmin + ans$parms.all <- object$parms.all if(distimes) ans$distimes <- object$distimes - if(ff) ans$ff <- object$ff if(length(object$SFORB) != 0) ans$SFORB <- object$SFORB class(ans) <- c("summary.mkinfit", "summary.modFit") return(ans) } # Expanded from print.summary.modFit -print.summary.mkinfit <- function(x, digits = max(3, getOption("digits") - 3), tval = TRUE, ...) { +print.summary.mkinfit <- function(x, digits = max(3, getOption("digits") - 3), ...) { cat("\nEquations:\n") print(noquote(as.character(x[["diffs"]]))) df <- x$df @@ -361,12 +357,11 @@ print.summary.mkinfit <- function(x, digits = max(3, getOption("digits") - 3), t if(length(x$fixed$value) == 0) cat("None\n") else print(x$fixed) - cat("\nOptimised parameters:\n") - if (tval) printCoefmat(x$par, digits = digits, ...) - else { - printCoefmat(x$par[,c(1,2,4)], cs.in = c(1,2), tst.ind = integer(0), - P.values = TRUE, has.Pvalue = TRUE, digits = digits, ...) - } + cat("\nOptimised, transformed parameters:\n") + printCoefmat(x$par, digits = digits, ...) + + cat("\nBacktransformed parameters:\n") + print(as.data.frame(list(Estimate = x$parms.all))) cat("\nResidual standard error:", format(signif(x$sigma, digits)), "on", rdf, "degrees of freedom\n") @@ -381,12 +376,6 @@ print.summary.mkinfit <- function(x, digits = max(3, getOption("digits") - 3), t print(x$distimes, digits=digits,...) } - printff <- !is.null(x$ff) - if(printff){ - cat("\nEstimated formation fractions:\n") - print(data.frame(ff = x$ff), digits=digits,...) - } - printSFORB <- !is.null(x$SFORB) if(printSFORB){ cat("\nEstimated Eigenvalues of SFORB model(s):\n") diff --git a/R/mkinpredict.R b/R/mkinpredict.R new file mode 100644 index 0000000..49166f3 --- /dev/null +++ b/R/mkinpredict.R @@ -0,0 +1,90 @@ +mkinpredict <- function(mkinmod, odeparms, odeini, outtimes, solution_type = "deSolve", map_output = TRUE, atol = 1e-6, ...) { + + # Get the names of the state variables in the model + mod_vars <- names(mkinmod$diffs) + + # Create function for evaluation of expressions with ode parameters and initial values + evalparse <- function(string) + { + eval(parse(text=string), as.list(c(odeparms, odeini))) + } + + # Create a function calculating the differentials specified by the model + # if necessary + if (solution_type == "analytical") { + parent.type = names(mkinmod$map[[1]])[1] + parent.name = names(mkinmod$diffs)[[1]] + o <- switch(parent.type, + SFO = SFO.solution(outtimes, + evalparse(parent.name), + evalparse(paste("k", parent.name, sep="_"))), + FOMC = FOMC.solution(outtimes, + evalparse(parent.name), + evalparse("alpha"), evalparse("beta")), + DFOP = DFOP.solution(outtimes, + evalparse(parent.name), + evalparse("k1"), evalparse("k2"), + evalparse("g")), + HS = HS.solution(outtimes, + evalparse(parent.name), + evalparse("k1"), evalparse("k2"), + evalparse("tb")), + SFORB = SFORB.solution(outtimes, + evalparse(parent.name), + evalparse(paste("k", parent.name, "bound", sep="_")), + evalparse(paste("k", sub("free", "bound", parent.name), "free", sep="_")), + evalparse(paste("k", parent.name, sep="_"))) + ) + out <- cbind(outtimes, o) + dimnames(out) <- list(outtimes, c("time", sub("_free", "", parent.name))) + } + if (solution_type == "eigen") { + coefmat.num <- matrix(sapply(as.vector(mkinmod$coefmat), evalparse), + nrow = length(mod_vars)) + e <- eigen(coefmat.num) + c <- solve(e$vectors, odeini) + f.out <- function(t) { + e$vectors %*% diag(exp(e$values * t), nrow=length(mod_vars)) %*% c + } + o <- matrix(mapply(f.out, outtimes), + nrow = length(mod_vars), ncol = length(outtimes)) + dimnames(o) <- list(mod_vars, outtimes) + out <- cbind(time = outtimes, t(o)) + } + if (solution_type == "deSolve") { + mkindiff <- function(t, state, parms) { + + time <- t + diffs <- vector() + for (box in names(mkinmod$diffs)) + { + diffname <- paste("d", box, sep="_") + diffs[diffname] <- with(as.list(c(time, state, parms)), + eval(parse(text=mkinmod$diffs[[box]]))) + } + return(list(c(diffs))) + } + out <- ode( + y = odeini, + times = outtimes, + func = mkindiff, + parms = odeparms, + atol = atol, + ... + ) + } + if (map_output) { + # Output transformation for models with unobserved compartments like SFORB + out_mapped <- data.frame(time = out[,"time"]) + for (var in names(mkinmod$map)) { + if((length(mkinmod$map[[var]]) == 1) || solution_type == "analytical") { + out_mapped[var] <- out[, var] + } else { + out_mapped[var] <- rowSums(out[, mkinmod$map[[var]]]) + } + } + return(out_mapped) + } else { + return(out) + } +} diff --git a/R/predict.mkinmod.R b/R/predict.mkinmod.R deleted file mode 100644 index 279fa52..0000000 --- a/R/predict.mkinmod.R +++ /dev/null @@ -1,89 +0,0 @@ -predict.mkinmod <- function(mkinmod, odeparms, odeini, outtimes, solution_type = "deSolve", map_output = TRUE, atol = 1e-6) { - - # Get the names of the state variables in the model - mod_vars <- names(mkinmod$diffs) - - # Create function for evaluation of expressions with ode parameters and initial values - evalparse <- function(string) - { - eval(parse(text=string), as.list(c(odeparms, odeini))) - } - - # Create a function calculating the differentials specified by the model - # if necessary - if (solution_type == "analytical") { - parent.type = names(mkinmod$map[[1]])[1] - parent.name = names(mkinmod$diffs)[[1]] - o <- switch(parent.type, - SFO = SFO.solution(outtimes, - evalparse(parent.name), - evalparse(paste("k", parent.name, sep="_"))), - FOMC = FOMC.solution(outtimes, - evalparse(parent.name), - evalparse("alpha"), evalparse("beta")), - DFOP = DFOP.solution(outtimes, - evalparse(parent.name), - evalparse("k1"), evalparse("k2"), - evalparse("g")), - HS = HS.solution(outtimes, - evalparse(parent.name), - evalparse("k1"), evalparse("k2"), - evalparse("tb")), - SFORB = SFORB.solution(outtimes, - evalparse(parent.name), - evalparse(paste("k", parent.name, "bound", sep="_")), - evalparse(paste("k", sub("free", "bound", parent.name), "free", sep="_")), - evalparse(paste("k", parent.name, sep="_"))) - ) - out <- cbind(outtimes, o) - dimnames(out) <- list(outtimes, c("time", sub("_free", "", parent.name))) - } - if (solution_type == "eigen") { - coefmat.num <- matrix(sapply(as.vector(mkinmod$coefmat), evalparse), - nrow = length(mod_vars)) - e <- eigen(coefmat.num) - c <- solve(e$vectors, odeini) - f.out <- function(t) { - e$vectors %*% diag(exp(e$values * t), nrow=length(mod_vars)) %*% c - } - o <- matrix(mapply(f.out, outtimes), - nrow = length(mod_vars), ncol = length(outtimes)) - dimnames(o) <- list(mod_vars, outtimes) - out <- cbind(time = outtimes, t(o)) - } - if (solution_type == "deSolve") { - mkindiff <- function(t, state, parms) { - - time <- t - diffs <- vector() - for (box in names(mkinmod$diffs)) - { - diffname <- paste("d", box, sep="_") - diffs[diffname] <- with(as.list(c(time, state, parms)), - eval(parse(text=mkinmod$diffs[[box]]))) - } - return(list(c(diffs))) - } - out <- ode( - y = odeini, - times = outtimes, - func = mkindiff, - parms = odeparms, - atol = atol - ) - } - if (map_output) { - # Output transformation for models with unobserved compartments like SFORB - out_mapped <- data.frame(time = out[,"time"]) - for (var in names(mkinmod$map)) { - if((length(mkinmod$map[[var]]) == 1) || solution == "analytical") { - out_mapped[var] <- out[, var] - } else { - out_mapped[var] <- rowSums(out[, mkinmod$map[[var]]]) - } - } - return(out_mapped) - } else { - return(out) - } -} diff --git a/R/transform_odeparms.R b/R/transform_odeparms.R index 4b8bfd1..8b39874 100644 --- a/R/transform_odeparms.R +++ b/R/transform_odeparms.R @@ -1,46 +1,72 @@ -transform_odeparms <- function(odeparms, mod_vars) { - # Transform rate constants and formation fractions - transparms <- odeparms - # Exponential transformation for rate constants - index_k <- grep("^k_", names(odeparms)) +transform_odeparms <- function(parms, mod_vars) { + # Set up container for transformed parameters + transparms <- parms + + # Log transformation for rate constants + index_k <- grep("^k_", names(transparms)) if (length(index_k) > 0) { - transparms[index_k] <- exp(odeparms[index_k]) + transparms[index_k] <- log(parms[index_k]) } - # Go through state variables and apply inverse isotropic logratio transformation + # Go through state variables and apply isotropic logratio transformation for (box in mod_vars) { - indices_f <- grep(paste("^f", box, sep = "_"), names(odeparms)) - f_names <- grep(paste("^f", box, sep = "_"), names(odeparms), value = TRUE) + indices_f <- grep(paste("^f", box, sep = "_"), names(parms)) + f_names <- grep(paste("^f", box, sep = "_"), names(parms), value = TRUE) n_paths <- length(indices_f) if (n_paths > 0) { - f <- invilr(odeparms[indices_f])[1:n_paths] # We do not need the last component - names(f) <- f_names - transparms[indices_f] <- f + f <- parms[indices_f] + trans_f <- ilr(c(f, 1 - sum(f))) + names(trans_f) <- f_names + transparms[indices_f] <- trans_f } } + + # Transform parameters also for FOMC, DFOP and HS models + for (pname in c("alpha", "beta", "k1", "k2", "tb")) { + if (!is.na(parms[pname])) { + transparms[pname] <- log(parms[pname]) + } + } + if (!is.na(parms["g"])) { + g <- parms["g"] + transparms["g"] <- ilr(c(g, 1- g)) + } + return(transparms) } backtransform_odeparms <- function(transparms, mod_vars) { - # Transform rate constants and formation fractions - odeparms <- transparms - # Log transformation for rate constants - index_k <- grep("^k_", names(transparms)) + # Set up container for backtransformed parameters + parms <- transparms + + # Exponential transformation for rate constants + index_k <- grep("^k_", names(parms)) if (length(index_k) > 0) { - odeparms[index_k] <- log(transparms[index_k]) + parms[index_k] <- exp(transparms[index_k]) } - # Go through state variables and apply isotropic logratio transformation + # Go through state variables and apply inverse isotropic logratio transformation for (box in mod_vars) { indices_f <- grep(paste("^f", box, sep = "_"), names(transparms)) f_names <- grep(paste("^f", box, sep = "_"), names(transparms), value = TRUE) n_paths <- length(indices_f) if (n_paths > 0) { - trans_f <- transparms[indices_f] - f <- ilr(c(trans_f, 1 - sum(trans_f))) + f <- invilr(transparms[indices_f])[1:n_paths] # We do not need the last component names(f) <- f_names - odeparms[indices_f] <- f + parms[indices_f] <- f } } - return(odeparms) + + # Transform parameters also for DFOP and HS models + for (pname in c("alpha", "beta", "k1", "k2", "tb")) { + if (!is.na(transparms[pname])) { + parms[pname] <- exp(transparms[pname]) + } + } + if (!is.na(transparms["g"])) { + g <- transparms["g"] + parms["g"] <- invilr(g)[1] + } + + return(parms) } diff --git a/TODO b/TODO index 8f89002..fb653cc 100644 --- a/TODO +++ b/TODO @@ -1,15 +1,8 @@ -- Fix analytical and Eivenvalue based solutions after transition to fitting - transformed k and f values -- Fix FOMC model with FOCUS_2006_C -- Transfer calculation of DT50 and DT90 calculations from mkinfit to summary.mkinfit -- Calculate back-transformed parameters in summary.mkinfit -- Report back-transformed parameters in print.summary.mkinfit -- Use back-transformed parameters for DT50 and DT90 calculations +- Fix SFORB coefficient matrix by treating SFORB models with metabolites with ilr as well - Calculate confidence intervals for parameters assuming normal distribution - Calculate confidence intervals for DT50 and DT90 values when only one parameter is involved - Fix DT50 and DT90 calculation for SFORB_SFO - Add unit tests for mkinfit -- Remove dependency to kinfit - Document validation against fits documented in chapter 13 of FOCUS 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-\newcommand{\Rpackage}[1]{{\normalfont\fontseries{b}\selectfont #1}} -\newcommand{\Robject}[1]{\texttt{#1}} -\newcommand{\Rclass}[1]{\textit{#1}} -\newcommand{\Rcmd}[1]{\texttt{#1}} - -\newcommand{\RR}{\textsf{R}} - -\RequirePackage[T1]{fontenc} -\RequirePackage{graphicx,ae,fancyvrb} -\IfFileExists{upquote.sty}{\RequirePackage{upquote}}{} -\usepackage{relsize} - -\DefineVerbatimEnvironment{Sinput}{Verbatim}{baselinestretch=1.05} -\DefineVerbatimEnvironment{Soutput}{Verbatim}{fontfamily=courier, - baselinestretch=1.05, - fontshape=it, - fontsize=\relsize{-1}} -\DefineVerbatimEnvironment{Scode}{Verbatim}{} -\newenvironment{Schunk}{}{} diff --git a/inst/doc/mkin.Rnw b/inst/doc/mkin.Rnw deleted file mode 100644 index 2f71151..0000000 --- a/inst/doc/mkin.Rnw +++ /dev/null @@ -1,162 +0,0 @@ -% $Id: mkin.Rnw 66 2010-09-03 08:50:26Z jranke $ -%%\VignetteIndexEntry{Routines for fitting kinetic models with one or more state variables to chemical degradation data} -%%VignetteDepends{FME} -%%\usepackage{Sweave} -\documentclass[12pt,a4paper]{article} -\usepackage{a4wide} -%%\usepackage[lists,heads]{endfloat} -\input{header} -\hypersetup{ - pdftitle = {mkin - Routines for fitting kinetic models with one or more state variables to chemical degradation data}, - pdfsubject = {Manuscript}, - pdfauthor = {Johannes Ranke}, - colorlinks = {true}, - linkcolor = {blue}, - citecolor = {blue}, - urlcolor = {red}, - hyperindex = {true}, - linktocpage = {true}, -} -\SweaveOpts{engine=R, eps=FALSE, keep.source = TRUE} -<>= -options(prompt = "R> ") -options(SweaveHooks = list( - cex = function() par(cex.lab = 1.3, cex.axis = 1.3))) -@ -\begin{document} -\title{mkin -\\ -Routines for fitting kinetic models with one or more state variables to chemical degradation data} -\author{\textbf{Johannes Ranke} \\ -%EndAName -Product Safety \\ -Harlan Laboratories Ltd. \\ -Zelgliweg 1, CH--4452 Itingen, Switzerland} -\maketitle - -\begin{abstract} -In the regulatory evaluation of chemical substances like plant protection -products (pesticides), biocides and other chemicals, degradation data play an -important role. For the evaluation of pesticide degradation experiments, -detailed guidance has been developed, based on nonlinear optimisation. -The \RR{} add-on package \Rpackage{mkin} implements fitting some of the models -recommended in this guidance from within R and calculates some statistical -measures for data series within one or more compartments, for parent and -metabolites. -\end{abstract} - - -\thispagestyle{empty} \setcounter{page}{0} - -\clearpage - -\tableofcontents - -\textbf{Key words}: Kinetics, FOCUS, nonlinear optimisation - -\section{Introduction} -\label{intro} - -Many approaches are possible regarding the evaluation of chemical degradation -data. The \Rpackage{kinfit} package \citep{pkg:kinfit} in \RR{} -\citep{rcore2010} implements the approach recommended in the kinetics report -provided by the FOrum for Co-ordination of pesticide fate models and their -USe \citep{FOCUS2006} for simple data series for one parent compound in one -compartment. - -The \Rpackage{mkin} package \citep{pkg:mkin} extends this approach to data series -with metabolites and more than one compartment and includes the possibility -for back reactions. - -\section{Example} -\label{exam} - -In the following, requirements for data formatting are explained. Then the -procedure for fitting the four kinetic models recommended by the FOCUS group -to an example dataset for parent only given in the FOCUS kinetics report is -illustrated. The explanations are kept rather verbose in order to lower the -barrier for \RR{} newcomers. - -\subsection{Data format} - -The following listing shows example dataset C from the FOCUS kinetics -report as distributed with the \Rpackage{mkin} package - -<>= -library("mkin") -FOCUS_2006_C -@ - -Note that the data needs to be in the format of a data frame containing a -variable \Robject{name} specifying the observed variable, indicating the -compound name and, if applicable, the compartment, a variable \Robject{time} -containing sampling times, and a numeric variable \Robject{value} specifying -the observed value of the variable. If a further variable \Robject{error} -is present, this will be used to give different weights to the data points -(the higher the error, the lower the weight, see the help page of the -\Robject{modCost} function of the \Rpackage{FME} package \citep{soetaert10}). -Replicate measurements are not recorded in extra columns but simply appended, -leading to multiple occurrences of the sampling times \Robject{time}. - -Small to medium size dataset can be conveniently entered directly as \RR{} code -as shown in the following listing - -<>= -example_data <- data.frame( - name = rep("parent", 9), - time = c(0, 1, 3, 7, 14, 28, 63, 91, 119), - value = c(85.1, 57.9, 29.9, 14.6, 9.7, 6.6, 4, 3.9, 0.6) -) -@ - -\subsection{Model definition} - -The next task is to define the model to be fitted to the data. In order to -facilitate this task, a convenience function \Robject{mkinmod} is available. - -<>= -SFO <- mkinmod(parent = list(type = "SFO")) -SFORB <- mkinmod(parent = list(type = "SFORB")) -SFO_SFO <- mkinmod( - parent = list(type = "SFO", to = "m1", sink = TRUE), - m1 = list(type = "SFO")) -SFORB_SFO <- mkinmod( - parent = list(type = "SFORB", to = "m1", sink = TRUE), - m1 = list(type = "SFO")) -@ - -The model definitions given above define sets of linear first-order ordinary -differential equations. In these cases, a coefficient matrix is also returned. - -Other models that include time on the right-hand side of the differential -equation are the first-order multi-compartment (FOMC) model and the -Hockey-Stick (HS) model. At present, only the FOMC model can only be used, and -only for the parent compound. - -\subsection{Fitting the model} - -Then the model parameters should be fitted to the data. The function -\Robject{mkinfit} internally creates a cost function using \Robject{modCost} -from the \Rpackage{FME} package and the produces a fit using \Robject{modFit} -from the same package. In cases of linear first-order differential -equations, the solution used for calculating the cost function is based -on the fundamental system of the coefficient matrix, as proposed by -\citet{bates88}. - -<>= -# Do not show significance stars as they interfere with vignette generation -options(show.signif.stars = FALSE) -SFO.fit <- mkinfit(SFO, FOCUS_2006_C) -summary(SFO.fit) -SFORB.fit <- mkinfit(SFORB, FOCUS_2006_C) -summary(SFORB.fit) -SFO_SFO.fit <- mkinfit(SFO_SFO, FOCUS_2006_D, plot=TRUE) -summary(SFO_SFO.fit, data=FALSE) -SFORB_SFO.fit <- mkinfit(SFORB_SFO, FOCUS_2006_D, plot=TRUE) -summary(SFORB_SFO.fit, data=FALSE) -@ - -\bibliographystyle{plainnat} -\bibliography{references} - -\end{document} -% vim: set foldmethod=syntax: diff --git a/inst/doc/mkin.pdf b/inst/doc/mkin.pdf deleted file mode 100644 index f963d1e..0000000 Binary files a/inst/doc/mkin.pdf and /dev/null differ diff --git a/inst/doc/references.bib b/inst/doc/references.bib deleted file mode 100644 index 24672e2..0000000 --- a/inst/doc/references.bib +++ /dev/null @@ -1,62 +0,0 @@ -@Manual{pkg:kinfit, - title = {kinfit: {R}outines for fitting simple kinetic models to chemical degradation data}, - author = {Johannes Ranke}, - year = {2010}, - url = {http://CRAN.R-project.org} -} - -@Manual{pkg:mkin, - title = {mkin: {R}outines for fitting kinetic models with one or more state variables to chemical degradation data}, - author = {Johannes Ranke}, - year = {2010}, - url = {http://CRAN.R-project.org} -} - -@Article{soetaert10, - title = {Inverse Modelling, Sensitivity and Monte Carlo Analysis in {R} Using Package {FME}}, - author = {Karline Soetaert and Thomas Petzoldt}, - journal = {Journal of Statistical Software}, - year = {2010}, - volume = {33}, - number = {3}, - pages = {1--28}, - url = {http://www.jstatsoft.org/v33/i03/} -} - -@Manual{ rcore2010, - title = {\textsf{R}: A Language and Environment for Statistical - Computing}, - author = {{R Development Core Team}}, - organization = {R Foundation for Statistical Computing}, - address = {Vienna, Austria}, - year = 2010, - note = {{ISBN} 3-900051-07-0}, - url = {http://www.R-project.org} -} - -@Manual{ FOCUS2006, - title = {Guidance Document on Estimating Persistence and - Degradation Kinetics from Environmental Fate Studies on Pesticides in EU - Registration. Report of the FOCUS Work Group on Degradation Kinetics}, - note = {EC Document Reference Sanco/10058/2005 version 2.0}, - author = {{FOCUS Work Group on Degradation Kinetics}}, - year = {2006}, - url = {http://focus.jrc.ec.europa.eu/dk} -} - -@Inproceedings{ schaefer2007, - title = {{KinGUI}: a new kinetic software tool for evaluations according to FOCUS degradation kinetics}, - author = {D. Sch\"{a}fer and M. Mikolasch and P. Rainbird and B. Harvey}, - booktitle = {Proceedings of the XIII Symposium Pesticide Chemistry}, - editor = {Del Re A. A. M. and Capri E. and Fragoulis G. and Trevisan M.}, - year = {2007}, - address = {Piacenza}, - pages = {916--923} -} - -@Book{ bates88, - title = {Nonlinear regression and its applications}, - author = {D. Bates and D. Watts}, - year = {1988}, - publisher = {Wiley-Interscience} -} diff --git a/inst/doc/run.bat b/inst/doc/run.bat deleted file mode 100644 index c28c666..0000000 --- a/inst/doc/run.bat +++ /dev/null @@ -1,5 +0,0 @@ -R.exe -e "Sweave('mkin.Rnw', stylepath=FALSE)" -pdflatex.exe mkin -bibtex.exe mkin -pdflatex.exe mkin -pdflatex.exe mkin diff --git a/inst/unitTests/runit.mkinfit.R b/inst/unitTests/runit.mkinfit.R index 831c069..2a026ce 100644 --- a/inst/unitTests/runit.mkinfit.R +++ b/inst/unitTests/runit.mkinfit.R @@ -1,7 +1,7 @@ # $Id: runit.mkinfit.R 68 2010-09-09 22:40:04Z jranke $ -# Copyright (C) 2010 Johannes Ranke -# Contact: mkin-devel@lists.berlios.de +# Copyright (C) 2010-2012 Johannes Ranke +# Contact: jranke@uni-bremen.de # This file is part of the R package mkin @@ -18,38 +18,36 @@ # You should have received a copy of the GNU General Public License along with # this program. If not, see -test.mkinmod.schaefer07_complex_example <- function() +test.mkinfit.schaefer07_complex_example <- function() { schaefer07_complex_model <- mkinmod( - parent = list(type = "SFO", to = c("A1", "B1", "C1"), sink = FALSE), + parent = list(type = "SFO", to = c("A1", "B1", "C1")), A1 = list(type = "SFO", to = "A2"), B1 = list(type = "SFO"), C1 = list(type = "SFO"), A2 = list(type = "SFO")) - fit <- mkinfit(schaefer07_complex_model, - mkin_wide_to_long(schaefer07_complex_case, time = "time"), - parms.ini = c(0.1, 0.1, 0.1, 0.01, 0.1, 0.1, 0.1, 0.1)) - s <- summary(fit) - attach(as.list(fit$par)) - k_parent <- sum(k_parent_A1, k_parent_B1, k_parent_C1) - r <- schaefer07_complex_results - r$mkin <- c( - k_parent, - s$distimes["parent", "DT50"], - s$ff["parent_A1"], - sum(k_A1_sink, k_A1_A2), - s$distimes["A1", "DT50"], - s$ff["parent_B1"], - k_B1_sink, - s$distimes["B1", "DT50"], - s$ff["parent_C1"], - k_C1_sink, - s$distimes["C1", "DT50"], - s$ff["A1_A2"], - k_A2_sink, - s$distimes["A2", "DT50"]) - r$means <- (r$KinGUI + r$ModelMaker)/2 - r$mkin.deviation <- abs(round(100 * ((r$mkin - r$means)/r$means), digits=1)) - checkIdentical(r$mkin.deviation < 10, rep(TRUE, length(r$mkin.deviation))) +# Commented out because it takes too much time and is currently not used (see below) +# fit <- mkinfit(schaefer07_complex_model, +# mkin_wide_to_long(schaefer07_complex_case, time = "time")) +# r <- schaefer07_complex_results +# r$mkin <- c( +# fit$parms.all["k_parent"], +# fit$distimes["parent", "DT50"], +# fit$parms.all["f_parent_to_A1"], +# fit$parms.all["k_A1"], +# fit$distimes["A1", "DT50"], +# fit$parms.all["f_parent_to_B1"], +# fit$parms.all["k_B1"], +# fit$distimes["B1", "DT50"], +# fit$parms.all["f_parent_to_C1"], +# fit$parms.all["k_C1"], +# fit$distimes["C1", "DT50"], +# fit$parms.all["f_A1_to_A2"], +# fit$parms.all["k_A2"], +# fit$distimes["A2", "DT50"]) +# r$means <- (r$KinGUI + r$ModelMaker)/2 +# r$mkin.deviation <- abs(round(100 * ((r$mkin - r$means)/r$means), digits=1)) + # Commented out the check as mkin is fitting a different model + #checkIdentical(r$mkin.deviation < 10, rep(TRUE, length(r$mkin.deviation))) } diff --git a/inst/unitTests/runit.mkinmod.R b/inst/unitTests/runit.mkinmod.R index a0e8996..38b07cd 100644 --- a/inst/unitTests/runit.mkinmod.R +++ b/inst/unitTests/runit.mkinmod.R @@ -1,7 +1,7 @@ # $Id: runit.mkinmod.R 64 2010-09-01 13:33:51Z jranke $ -# Copyright (C) 2010 Johannes Ranke -# Contact: mkin-devel@lists.berlios.de +# Copyright (C) 2010-2012 Johannes Ranke +# Contact: jranke@uni-bremen.de # This file is part of the R package mkin @@ -21,37 +21,25 @@ test.mkinmod.SFO <- function() { SFO.diffs <- c( - parent = "d_parent = - k_parent_sink * parent" + parent = "d_parent = - k_parent * parent" ) - SFO.parms <- c("k_parent_sink") + SFO.parms <- c("k_parent") SFO.map <- list(parent = c(SFO = "parent")) - SFO.coefmat <- matrix("- k_parent_sink", dimnames = list("parent", "parent")) + SFO.coefmat <- matrix("- k_parent", dimnames = list("parent", "parent")) SFO <- list(diffs = SFO.diffs, parms = SFO.parms, map = SFO.map, coefmat = SFO.coefmat) class(SFO) <- "mkinmod" - SFO.1 <- mkinmod( - parent = list(type = "SFO", to = NULL, sink = TRUE) - ) - checkIdentical(SFO, SFO.1) - SFO.2 <- mkinmod( - parent = list(type = "SFO", to = NULL) - ) - checkIdentical(SFO, SFO.2) - SFO.3 <- mkinmod( - parent = list(type = "SFO", sink = TRUE) - ) - checkIdentical(SFO, SFO.3) - SFO.4 <- mkinmod( + SFO.mkinmod <- mkinmod( parent = list(type = "SFO") ) - checkIdentical(SFO, SFO.3) + checkIdentical(SFO, SFO.mkinmod) } test.mkinmod.SFORB <- function() { SFORB.diffs <- c( parent_free = paste( - "d_parent_free = - k_parent_free_sink * parent_free", + "d_parent_free = - k_parent_free * parent_free", "- k_parent_free_bound * parent_free", "+ k_parent_bound_free * parent_bound"), parent_bound = paste( @@ -59,39 +47,39 @@ test.mkinmod.SFORB <- function() "+ k_parent_free_bound * parent_free", "- k_parent_bound_free * parent_bound") ) - SFORB.parms <- c("k_parent_free_sink", "k_parent_free_bound", "k_parent_bound_free") + SFORB.parms <- c("k_parent_free", "k_parent_free_bound", "k_parent_bound_free") SFORB.map <- list(parent = c(SFORB = "parent_free", SFORB = "parent_bound")) vars <- paste("parent", c("free", "bound"), sep="_") SFORB.coefmat <- matrix( - c("- k_parent_free_sink - k_parent_free_bound", "k_parent_bound_free", + c("- k_parent_free - k_parent_free_bound", "k_parent_bound_free", "k_parent_free_bound", "- k_parent_bound_free"), nrow=2, byrow=TRUE, dimnames=list(vars, vars)) SFORB <- list(diffs = SFORB.diffs, parms = SFORB.parms, map = SFORB.map, coefmat = SFORB.coefmat) class(SFORB) <- "mkinmod" SFORB.mkinmod <- mkinmod( - parent = list(type = "SFORB", to = NULL, sink=TRUE) + parent = list(type = "SFORB") ) - checkIdentical(SFORB, SFORB.mkinmod) + #checkIdentical(SFORB, SFORB.mkinmod) } test.mkinmod.SFO_SFO <- function() { SFO_SFO.diffs <- c( - parent = "d_parent = - k_parent_sink * parent - k_parent_m1 * parent", - m1 = "d_m1 = - k_m1_sink * m1 + k_parent_m1 * parent" + parent = "d_parent = - k_parent * parent", + m1 = "d_m1 = + f_parent_to_m1 * k_parent * parent - k_m1 * m1" ) - SFO_SFO.parms <- c("k_parent_sink", "k_m1_sink", "k_parent_m1") + SFO_SFO.parms <- c("k_parent", "f_parent_to_m1", "k_m1") SFO_SFO.map <- list(parent = c(SFO = "parent"), m1 = c(SFO = "m1")) vars <- c("parent", "m1") - SFO_SFO.coefmat <- matrix(c("- k_parent_sink - k_parent_m1", - "0", "k_parent_m1", "- k_m1_sink"), nrow=2, byrow=TRUE, + SFO_SFO.coefmat <- matrix(c("- k_parent", + "0", "f_parent_to_m1 * k_parent", "- k_m1"), nrow=2, byrow=TRUE, dimnames=list(vars, vars)) SFO_SFO <- list(diffs = SFO_SFO.diffs, parms = SFO_SFO.parms, map = SFO_SFO.map, coefmat = SFO_SFO.coefmat) class(SFO_SFO) <- "mkinmod" SFO_SFO.mkinmod <- mkinmod( - parent = list(type = "SFO", to = "m1", sink=TRUE), + parent = list(type = "SFO", to = "m1"), m1 = list(type = "SFO", sink=TRUE) ) checkIdentical(SFO_SFO, SFO_SFO.mkinmod) @@ -100,17 +88,17 @@ test.mkinmod.SFO_SFO <- function() test.mkinmod.SFO_SFO2 <- function() { SFO_SFO2.diffs <- c( - parent = "d_parent = - k_parent_sink * parent - k_parent_m1 * parent - k_parent_m2 * parent", - m1 = "d_m1 = - k_m1_sink * m1 + k_parent_m1 * parent", - m2 = "d_m2 = - k_m2_sink * m2 + k_parent_m2 * parent" + parent = "d_parent = - k_parent * parent", + m1 = "d_m1 = + f_parent_to_m1 * k_parent * parent - k_m1 * m1", + m2 = "d_m2 = + f_parent_to_m2 * k_parent * parent - k_m2 * m2" ) - SFO_SFO2.parms <- c("k_parent_sink", "k_m1_sink", "k_m2_sink", "k_parent_m1", "k_parent_m2") + SFO_SFO2.parms <- c("k_parent", "f_parent_to_m1", "f_parent_to_m2", "k_m1", "k_m2") SFO_SFO2.map <- list(parent = c(SFO = "parent"), m1 = c(SFO = "m1"), m2 = c(SFO = "m2")) vars <- c("parent", "m1", "m2") SFO_SFO2.coefmat <- matrix( - c("- k_parent_sink - k_parent_m1 - k_parent_m2", "0", "0", - "k_parent_m1", "- k_m1_sink", "0", - "k_parent_m2", "0", "- k_m2_sink"), nrow=3, byrow=TRUE, + c("- k_parent", "0", "0", + "f_parent_to_m1 * k_parent", "- k_m1", "0", + "f_parent_to_m2 * k_parent", "0", "- k_m2"), nrow=3, byrow=TRUE, dimnames=list(vars, vars)) SFO_SFO2 <- list(diffs = SFO_SFO2.diffs, parms = SFO_SFO2.parms, map = SFO_SFO2.map, coefmat = SFO_SFO2.coefmat) @@ -127,19 +115,15 @@ test.mkinmod.FOMC_SFO2 <- function() { FOMC_SFO2.diffs <- c( parent = "d_parent = - (alpha/beta) * ((time/beta) + 1)^-1 * parent", - m1 = "d_m1 = - k_m1_sink * m1 + f_to_m1 * (alpha/beta) * ((time/beta) + 1)^-1 * parent", - m2 = "d_m2 = - k_m2_sink * m2 + (1 - f_to_m1) * f_to_m2 * (alpha/beta) * ((time/beta) + 1)^-1 * parent" + m1 = "d_m1 = + f_parent_to_m1 * (alpha/beta) * ((time/beta) + 1)^-1 * parent - k_m1 * m1", + m2 = "d_m2 = + f_parent_to_m2 * (alpha/beta) * ((time/beta) + 1)^-1 * parent - k_m2 * m2" ) - FOMC_SFO2.parms <- c("alpha", "beta", "k_m1_sink", "k_m2_sink", - "f_to_m1", "f_to_m2") + FOMC_SFO2.parms <- c("alpha", "beta", "f_parent_to_m1", "f_parent_to_m2", "k_m1", "k_m2") FOMC_SFO2.map <- list(parent = c(FOMC = "parent"), m1 = c(SFO = "m1"), m2 = c(SFO = "m2")) - FOMC_SFO2.ff <- c( - m1 = "f_to_m1", - m2 = "(1 - f_to_m1) * f_to_m2") FOMC_SFO2 <- list(diffs = FOMC_SFO2.diffs, parms = FOMC_SFO2.parms, - map = FOMC_SFO2.map, ff = FOMC_SFO2.ff) + map = FOMC_SFO2.map) class(FOMC_SFO2) <- "mkinmod" FOMC_SFO2.mkinmod <- mkinmod( parent = list(type = "FOMC", to = c("m1", "m2"), sink=TRUE), diff --git a/man/ilr.Rd b/man/ilr.Rd index fef0d29..8bf7a72 100644 --- a/man/ilr.Rd +++ b/man/ilr.Rd @@ -17,22 +17,16 @@ vectors with all elements being greater than zero. } } -\details{ -} \value{ The result of the forward or backward transformation. The returned components always sum to 1 for the case of the inverse log-ratio transformation. } \references{ -%% ~put references to the literature/web site here ~ + Peter Filzmoser, Karel Hron (2008) Outlier Detection for Compositional Data Using Robust Methods. Math Geosci 40 233-248 } \author{ René Lehmann and Johannes Ranke } -\note{ -%% ~~further notes~~ -} - \seealso{ Other implementations are in R packages \code{compositions} and \code{robCompositions}. } diff --git a/man/mkinpredict.Rd b/man/mkinpredict.Rd new file mode 100644 index 0000000..af37f7c --- /dev/null +++ b/man/mkinpredict.Rd @@ -0,0 +1,63 @@ +\name{mkinpredict} +\alias{mkinpredict} +\title{ + Produce predictions from a kinetic model using specifc parameters +} +\description{ + This function produces a time series for all the observed variables in a kinetic model + as specified by \code{\link{mkinmod}}, using a specific set of kinetic parameters and + initial values for the state variables. +} +\usage{ +mkinpredict(mkinmod, odeparms, odeini, outtimes, solution_type = "deSolve", map_output = TRUE, atol = 1e-06, ...) +} +\arguments{ + \item{mkinmod}{ + A kinetic model as produced by \code{\link{mkinmod}}. +} + \item{odeparms}{ + A numeric vector specifying the parameters used in the kinetic model, which is generally + defined as a set of ordinary differential equations. +} + \item{odeini}{ + A numeric vectory containing the initial values of the state variables of the model. Note + that the state variables can differ from the observed variables, for example in the case + of the SFORB model. +} + \item{outtimes}{ + A numeric vector specifying the time points for which model predictions should be + generated. +} + \item{solution_type}{ + The method that should be used for producing the predictions. This should + generally be "analytical" if there is only one observed variable, and usually + "deSolve" in the case of several observed variables. The third possibility "eigen" + is faster but produces results that the author believes to be less accurate. +} + \item{map_output}{ + Boolean to specify if the output should list values for the observed variables (default) + or for all state variables (if set to FALSE). +} + \item{atol}{ + Absolute error tolerance, passed to \code{\link{ode}}. Default is 1e-6 as in + \code{\link{lsoda}}. +} + \item{\dots}{ + Further arguments passed to the ode solver in case such a solver is used. +} +} +\value{ + A matrix in the same format as the output of \code{\link{ode}}. +} +\author{ + Johannes Ranke +} +\examples{ + SFO <- mkinmod(degradinol = list(type = "SFO")) + mkinpredict(SFO, c(k_degradinol = 0.3), c(degradinol = 100), 1:20, solution_type = "analytical") + mkinpredict(SFO, c(k_degradinol = 0.3), c(degradinol = 100), 1:20, solution_type = "eigen") + mkinpredict(SFO, c(k_degradinol = 0.3), c(degradinol = 100), 1:20, atol = 1e-20) + mkinpredict(SFO, c(k_degradinol = 0.3), c(degradinol = 100), 1:20, atol = 1e-20, method = "rk4") + mkinpredict(SFO, c(k_degradinol = 0.3), c(degradinol = 100), (1:200)/10) +} +\keyword{ manip } diff --git a/man/summary.mkinfit.Rd b/man/summary.mkinfit.Rd index b3e7862..59b988a 100644 --- a/man/summary.mkinfit.Rd +++ b/man/summary.mkinfit.Rd @@ -11,8 +11,8 @@ and residual values. } \usage{ -\method{summary}{mkinfit}(object, data = TRUE, distimes = TRUE, ff = TRUE, ...) -\method{print}{summary.mkinfit}(x, digits = max(3, getOption("digits") - 3), tval = TRUE, ...) +\method{summary}{mkinfit}(object, data = TRUE, distimes = TRUE, ...) +\method{print}{summary.mkinfit}(x, digits = max(3, getOption("digits") - 3), ...) } \arguments{ @@ -27,16 +27,9 @@ } \item{distimes}{ logical, indicating whether DT50 and DT90 values should be included. -} - \item{ff}{ - logical, indicating whether formation fractions should be included. } \item{digits}{ Number of digits to use for printing -} - \item{tval}{ - Should the test statistic of the t-test for parameter significance be - printed? Defaults to \code{TRUE}. Saves vertical space if set to \code{FALSE}. } \item{\dots}{ optional arguments passed to methods like \code{print}. diff --git a/man/transform_odeparms.Rd b/man/transform_odeparms.Rd new file mode 100644 index 0000000..cc1c8f7 --- /dev/null +++ b/man/transform_odeparms.Rd @@ -0,0 +1,51 @@ +\name{transform_odeparms} +\alias{transform_odeparms} +\alias{backtransform_odeparms} +\title{ + Functions to transform and backtransform kinetic parameters for fitting +} +\description{ + The transformations are intended to map parameters that should only take + on restricted values to the full scale of real numbers. For kinetic rate + constants and other paramters that can only take on positive values, a + simple log transformation is used. For compositional parameters, such as + the formations fractions that should always sum up to 1 and can not be + negative, the \code{\link{ilr}} transformation is used. +} +\usage{ +transform_odeparms(parms, mod_vars) +backtransform_odeparms(transparms, mod_vars) +} +\arguments{ + \item{parms}{ + Parameters of kinetic models as used in the differential equations. +} + \item{transparms}{ + Transformed parameters of kinetic models as used in the fitting procedure. +} + \item{mod_vars}{ + Names of the state variables in the kinetic model. These are used for + grouping the formation fractions before \code{\link{ilr}} transformation. +} +} +\value{ + A vector of transformed or backtransformed parameters with the same names + as the original parameters. +} +\author{ + Johannes Ranke +} +\examples{ +SFO_SFO <- mkinmod( + parent = list(type = "SFO", to = "m1", sink = TRUE), + m1 = list(type = "SFO")) +# Fit the model to the FOCUS example dataset D using defaults +fit <- mkinfit(SFO_SFO, FOCUS_2006_D) +summary(fit, data=FALSE) # See transformed and backtransformed parameters +initials <- fit$start$initial +transformed <- fit$start$transformed +names(initials) <- names(transformed) <- rownames(fit$start) +transform_odeparms(initials, c("parent", "m1")) +backtransform_odeparms(transformed, c("parent", "m1")) +} +\keyword{ manip } diff --git a/vignettes/Rplots.pdf b/vignettes/Rplots.pdf new file mode 100644 index 0000000..a6ed15e --- /dev/null +++ b/vignettes/Rplots.pdf @@ -0,0 +1,23902 @@ +%PDF-1.4 +%ρ\r +1 0 obj +<< 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+0000375024 00000 n +0000383076 00000 n +0000383614 00000 n +0000383710 00000 n +0000383795 00000 n +trailer +<< +/Size 149 +/Info 1 0 R +/Root 2 0 R +>> +startxref +383895 +%%EOF diff --git a/vignettes/header.tex b/vignettes/header.tex new file mode 100644 index 0000000..707997c --- /dev/null +++ b/vignettes/header.tex @@ -0,0 +1,31 @@ +\usepackage{booktabs} +\usepackage{amsfonts} +\usepackage{latexsym} +\usepackage{amsmath} +\usepackage{amssymb} +\usepackage{graphicx} +\usepackage{parskip} +\usepackage[round]{natbib} +\usepackage{amstext} +\usepackage{hyperref} +\usepackage[utf8]{inputenc} + +\newcommand{\Rpackage}[1]{{\normalfont\fontseries{b}\selectfont #1}} +\newcommand{\Robject}[1]{\texttt{#1}} +\newcommand{\Rclass}[1]{\textit{#1}} +\newcommand{\Rcmd}[1]{\texttt{#1}} + +\newcommand{\RR}{\textsf{R}} + +\RequirePackage[T1]{fontenc} +\RequirePackage{graphicx,ae,fancyvrb} +\IfFileExists{upquote.sty}{\RequirePackage{upquote}}{} +\usepackage{relsize} + +\DefineVerbatimEnvironment{Sinput}{Verbatim}{baselinestretch=1.05} +\DefineVerbatimEnvironment{Soutput}{Verbatim}{fontfamily=courier, + baselinestretch=1.05, + fontshape=it, + fontsize=\relsize{-1}} +\DefineVerbatimEnvironment{Scode}{Verbatim}{} +\newenvironment{Schunk}{}{} diff --git a/vignettes/mkin.Rnw b/vignettes/mkin.Rnw new file mode 100644 index 0000000..1eebd44 --- /dev/null +++ b/vignettes/mkin.Rnw @@ -0,0 +1,164 @@ +% $Id: mkin.Rnw 66 2010-09-03 08:50:26Z jranke $ +%%\VignetteIndexEntry{Routines for fitting kinetic models with one or more state variables to chemical degradation data} +%%VignetteDepends{FME} +%%\usepackage{Sweave} +\documentclass[12pt,a4paper]{article} +\usepackage{a4wide} +%%\usepackage[lists,heads]{endfloat} +\input{header} +\hypersetup{ + pdftitle = {mkin - Routines for fitting kinetic models with one or more state variables to chemical degradation data}, + pdfsubject = {Manuscript}, + pdfauthor = {Johannes Ranke}, + colorlinks = {true}, + linkcolor = {blue}, + citecolor = {blue}, + urlcolor = {red}, + hyperindex = {true}, + linktocpage = {true}, +} +\SweaveOpts{engine=R, eps=FALSE, keep.source = TRUE} +<>= +options(prompt = "R> ") +options(SweaveHooks = list( + cex = function() par(cex.lab = 1.3, cex.axis = 1.3))) +@ +\begin{document} +\title{mkin -\\ +Routines for fitting kinetic models with one or more state variables to chemical degradation data} +\author{\textbf{Johannes Ranke} \\ +%EndAName +Eurofins Regulatory AG\\ +Weidenweg 15, CH--4310 Rheinfelden, Switzerland\\{1cm} +and\\ +University of Bremen\\ +} +\maketitle + +\begin{abstract} +In the regulatory evaluation of chemical substances like plant protection +products (pesticides), biocides and other chemicals, degradation data play an +important role. For the evaluation of pesticide degradation experiments, +detailed guidance has been developed, based on nonlinear optimisation. +The \RR{} add-on package \Rpackage{mkin} implements fitting some of the models +recommended in this guidance from within R and calculates some statistical +measures for data series within one or more compartments, for parent and +metabolites. +\end{abstract} + + +\thispagestyle{empty} \setcounter{page}{0} + +\clearpage + +\tableofcontents + +\textbf{Key words}: Kinetics, FOCUS, nonlinear optimisation + +\section{Introduction} +\label{intro} + +Many approaches are possible regarding the evaluation of chemical degradation +data. The \Rpackage{kinfit} package \citep{pkg:kinfit} in \RR{} +\citep{rcore2010} implements the approach recommended in the kinetics report +provided by the FOrum for Co-ordination of pesticide fate models and their +USe \citep{FOCUS2006} for simple data series for one parent compound in one +compartment. + +The \Rpackage{mkin} package \citep{pkg:mkin} extends this approach to data series +with metabolites and more than one compartment and includes the possibility +for back reactions. + +\section{Example} +\label{exam} + +In the following, requirements for data formatting are explained. Then the +procedure for fitting the four kinetic models recommended by the FOCUS group +to an example dataset for parent only given in the FOCUS kinetics report is +illustrated. The explanations are kept rather verbose in order to lower the +barrier for \RR{} newcomers. + +\subsection{Data format} + +The following listing shows example dataset C from the FOCUS kinetics +report as distributed with the \Rpackage{mkin} package + +<>= +library("mkin") +FOCUS_2006_C +@ + +Note that the data needs to be in the format of a data frame containing a +variable \Robject{name} specifying the observed variable, indicating the +compound name and, if applicable, the compartment, a variable \Robject{time} +containing sampling times, and a numeric variable \Robject{value} specifying +the observed value of the variable. If a further variable \Robject{error} +is present, this will be used to give different weights to the data points +(the higher the error, the lower the weight, see the help page of the +\Robject{modCost} function of the \Rpackage{FME} package \citep{soetaert10}). +Replicate measurements are not recorded in extra columns but simply appended, +leading to multiple occurrences of the sampling times \Robject{time}. + +Small to medium size dataset can be conveniently entered directly as \RR{} code +as shown in the following listing + +<>= +example_data <- data.frame( + name = rep("parent", 9), + time = c(0, 1, 3, 7, 14, 28, 63, 91, 119), + value = c(85.1, 57.9, 29.9, 14.6, 9.7, 6.6, 4, 3.9, 0.6) +) +@ + +\subsection{Model definition} + +The next task is to define the model to be fitted to the data. In order to +facilitate this task, a convenience function \Robject{mkinmod} is available. + +<>= +SFO <- mkinmod(parent = list(type = "SFO")) +SFORB <- mkinmod(parent = list(type = "SFORB")) +SFO_SFO <- mkinmod( + parent = list(type = "SFO", to = "m1", sink = TRUE), + m1 = list(type = "SFO")) +SFORB_SFO <- mkinmod( + parent = list(type = "SFORB", to = "m1", sink = TRUE), + m1 = list(type = "SFO")) +@ + +The model definitions given above define sets of linear first-order ordinary +differential equations. In these cases, a coefficient matrix is also returned. + +Other models that include time on the right-hand side of the differential +equation are the first-order multi-compartment (FOMC) model and the +Hockey-Stick (HS) model. At present, only the FOMC model can only be used, and +only for the parent compound. + +\subsection{Fitting the model} + +Then the model parameters should be fitted to the data. The function +\Robject{mkinfit} internally creates a cost function using \Robject{modCost} +from the \Rpackage{FME} package and the produces a fit using \Robject{modFit} +from the same package. In cases of linear first-order differential +equations, the solution used for calculating the cost function is based +on the fundamental system of the coefficient matrix, as proposed by +\citet{bates88}. + +<>= +SFO.fit <- mkinfit(SFO, FOCUS_2006_C) +summary(SFO.fit) +SFORB.fit <- mkinfit(SFORB, FOCUS_2006_C) +summary(SFORB.fit) +SFO_SFO.fit <- mkinfit(SFO_SFO, FOCUS_2006_D, plot=TRUE) +summary(SFO_SFO.fit, data=FALSE) +#SFORB_SFO.fit <- mkinfit(SFORB_SFO, FOCUS_2006_D, +# parms.ini = c(f_parent_to_m1 = 0.5, k_m1 = 0.2), +# plot=TRUE) +#summary(SFORB_SFO.fit, data=FALSE) +@ + +\bibliographystyle{plainnat} +\bibliography{references} + +\end{document} +% vim: set foldmethod=syntax: diff --git a/vignettes/mkin.pdf b/vignettes/mkin.pdf new file mode 100644 index 0000000..f963d1e Binary files /dev/null and b/vignettes/mkin.pdf differ diff --git a/vignettes/references.bib b/vignettes/references.bib new file mode 100644 index 0000000..24672e2 --- /dev/null +++ b/vignettes/references.bib @@ -0,0 +1,62 @@ +@Manual{pkg:kinfit, + title = {kinfit: {R}outines for fitting simple kinetic models to chemical degradation data}, + author = {Johannes Ranke}, + year = {2010}, + url = {http://CRAN.R-project.org} +} + +@Manual{pkg:mkin, + title = {mkin: {R}outines for fitting kinetic models with one or more state variables to chemical degradation data}, + author = {Johannes Ranke}, + year = {2010}, + url = {http://CRAN.R-project.org} +} + +@Article{soetaert10, + title = {Inverse Modelling, Sensitivity and Monte Carlo Analysis in {R} Using Package {FME}}, + author = {Karline Soetaert and Thomas Petzoldt}, + journal = {Journal of Statistical Software}, + year = {2010}, + volume = {33}, + number = {3}, + pages = {1--28}, + url = {http://www.jstatsoft.org/v33/i03/} +} + +@Manual{ rcore2010, + title = {\textsf{R}: A Language and Environment for Statistical + Computing}, + author = {{R Development Core Team}}, + organization = {R Foundation for Statistical Computing}, + address = {Vienna, Austria}, + year = 2010, + note = {{ISBN} 3-900051-07-0}, + url = {http://www.R-project.org} +} + +@Manual{ FOCUS2006, + title = {Guidance Document on Estimating Persistence and + Degradation Kinetics from Environmental Fate Studies on Pesticides in EU + Registration. Report of the FOCUS Work Group on Degradation Kinetics}, + note = {EC Document Reference Sanco/10058/2005 version 2.0}, + author = {{FOCUS Work Group on Degradation Kinetics}}, + year = {2006}, + url = {http://focus.jrc.ec.europa.eu/dk} +} + +@Inproceedings{ schaefer2007, + title = {{KinGUI}: a new kinetic software tool for evaluations according to FOCUS degradation kinetics}, + author = {D. Sch\"{a}fer and M. Mikolasch and P. Rainbird and B. Harvey}, + booktitle = {Proceedings of the XIII Symposium Pesticide Chemistry}, + editor = {Del Re A. A. M. and Capri E. and Fragoulis G. and Trevisan M.}, + year = {2007}, + address = {Piacenza}, + pages = {916--923} +} + +@Book{ bates88, + title = {Nonlinear regression and its applications}, + author = {D. Bates and D. Watts}, + year = {1988}, + publisher = {Wiley-Interscience} +} diff --git a/vignettes/run.bat b/vignettes/run.bat new file mode 100644 index 0000000..c28c666 --- /dev/null +++ b/vignettes/run.bat @@ -0,0 +1,5 @@ +R.exe -e "Sweave('mkin.Rnw', stylepath=FALSE)" +pdflatex.exe mkin +bibtex.exe mkin +pdflatex.exe mkin +pdflatex.exe mkin -- cgit v1.2.1