Documente Academic
Documente Profesional
Documente Cultură
Abstract
Most regulations, if not all, include limits to heavy metals, many include limits for
pathogenic organisms and only very few for organic pollutants and only a very reduced
number of them. As regulations from member states of the EU implement the limits set in
Directive 86/278/EEC, either identically or more stringently, so too do some American
countries implement limits and requirements set by U.S EPA’s Part 503, though with slight
variations in each country.
1.- Introduction
Persistent organic pollutants are organic chemicals which may remain unaltered during
prolonged periods of time in different environmental compartments (Jones et al., 1999). They
usually have hydrophobic nature and tend to associate with the solid fraction in wastewater
and during wastewater treatment they concentrate in the sludge (Smith, 2009). Sludge
disposal has become an increasingly restricted activity with ocean dumping banned and
stringent regulations regulating other options. Land disposal and incineration have become
two of the most used strategies to deal with sludge. Land application in agriculture is another
frequent method of dealing with sludge that has shown many benefits as a soil improver and
natural fertilizer (Singh & Agrawal, 2008). Current regulations for land application of sludge are
based mostly on the contents of heavy metals, pathogens and the agronomic value of sludge,
while only few include organic pollutants and only a reduced part of all the ones that might be
present in sludge. Furthermore, there is evidence that suggests there may be uptake of organic
pollutants by crops grown in contaminated soils (Mueller et al., 2006; Huang et al., 2010;
Vrkoslavová et al., 2010; Huang et al., 2011). Therefore it is of great relevance to determine
the content of pollutants in sludge destined for land application; however, sludge, as other
complex matrices, poses challenging difficulties in the analysis of pollutants in trace amounts
due to the high content of interfering substances unavoidably co-extracted during sample
extraction. For this reason, the main objective of this research stay was to get familiarized with
the techniques developed by the research group in Tongji University to extract, clean-up and
analyze brominated flame retardants (PBDE’s) in sewage sludge. Furthermore, a detailed
analysis of the regulations for soil application of sewage sludge was conducted to identify
similarities and differences between different countries in America and Europe.
A sludge sample was collected at Cerro de la Estrella WWTP in Mexico City. Sample
pretreatment, extraction, clean-up and analysis was done following the procedure described
by Xiang et al. (2013). The sample was lyophilized to complete dryness and transported to
China. For extraction, 0.5g were weighted and introduced in previously Soxhlet-extracted filter
paper (Figure 1.a), samples were extracted using Soxhlet extraction with dichloromethane for
48 hours (Figure 1.b). Recovery standards were added to the extraction solvent. Analytes
where then transferred to hexane and lipids were removed by adding concentrated H2SO4
(Figure 1.c). Further extract clean-up was conducted using gel permeation chromatography
with dichloromethane:hexane as mobile phase (Figure 1.d). Sulfur was removed by adding
activated copper (Figure 1.e). Clean extracts were transferred to chromatography vials.
Chromatographic analysis and PBDE’s quantification was done by GC-MS.
a b c
d e
U.S. EPA 40 CFR Part 503 and Council Directive 86/278/EEC were analyzed in detail
regarding land application of sludge for agriculture. Following this initial comparison, other
countries of America and Europe were selected to compare their regulations against Part 503
and Directive 86/278/EEC. In America selected countries were Mexico, Argentina, Brazil and
Chile. In Europe, following a 2001 report by the European Commission that grouped member
states in three categories (similar, more stringent, and much more stringent), selected
countries were Spain, France and the Netherlands. Limits for heavy metals and pathogenic
organisms were compared as well as the length of temporal restrictions following sludge
amendment. Management practices proposed by each regulation were also considered.
3.- Results
Being this the analysis of just one grab sample and not having been able to make
corrections with internal standards, these results are preliminary and serve only as a rough
comparison.
100%
98%
~BDE Congener Average ± SD [ng/g]
BDE-17 4.934 ± 2.806
Tri BDE-28 4.549 ± 1.669
BDE-33 5.442 ± 0.601 96%
BDE-47 251.697 ± 20.044
Tri
Tetra BDE-49 10.978 ± 0.145
BDE-66 47.711 ± 33.737 Tetra
94%
BDE-99 302.764 ± 17.956
Penta Penta
BDE-100 60.288 ± 3.843
BDE-138 4.282 ± 0.371 Hexa
Hexa BDE-153 43.307 ± 1.747 92%
BDE-154 23.199 ± 1.111 Hepta
BDE-183 10.626 ± 0.557
Hepta Octa
BDE-190 0.45 ± 0.521
BDE-196 30.91 ± 2.277 90% Nona
Octa
BDE-203 118.23 ± 69.4
BDE-206 321.641 ± 40.266
Deca
Nona BDE-207 203.855 ± 82.632
88%
BDE-208 134.665 ± 0
Deca BDE-209 13,191.95 ± 3,470.127
Table 1 - Concentrations of PBDE congeners in
Mexican sludge sample 86%
84%
Shanghai Mexico
Though regulating less heavy metals than Part 503, Directive 86/278/EEC’s limits are
more stringent; however, it does not contain limits for pathogenic organisms and the
management practices it considers are minimal. Temporal restrictions set forth by Part 503 are
much more stringent, however they only apply to sludge with a high content of pathogenic
organisms while those of Directive 86/278/EEC apply to any kind of sludge. Part 503 describes
several options to reduce densities of pathogenic organisms and stabilize sludge while
Directive 86/278/EEC does not and only states it shall be treated before it’s used. Monitoring
demanded by Part 503 is clearly determined based on the amount of sludge applied or
prepared but only considers monitoring of sludge and not the land to which it is applied.
Monitoring according to Directive 86/278/EEC is more lax and does not depend on the amount
of sludge produced. Directive 86/278/EEC also considers monitoring of soil to which sludge is
applied but sets no specific frequency as this is left for member states to decide.
Other American regulations considered have mostly taken the model set by Part 503
while they may also incorporate some elements from European regulations (Argentinean and
Chilean regulations) and other management practices set by each country as well as variation
in the limits set for heavy metals and pathogenic organisms. Regarding heavy metals, the most
stringent limits are set by Chilean regulation and the laxest are those of Mexican regulation,
which copies those set by Part 503. Argentinean regulation is the only one that explicitly sets
limits for PCB’s. Brazilian regulation also requires analysis for several organic pollutants but the
limit for their concentration is not set for sludge but for soil. Argentinean and Chilean
regulations consider limits for heavy metals in soil prior to amendment, these are more
stringent in Chilean regulation where soil pH is also taken into account. All other American
regulations adopt the biosolid class system set by Part 503 with Mexican regulation adding an
additional “Class C” with significantly higher limits for pathogenic organisms. All but Mexican
regulation adopt temporal restrictions after application of sludge to land. Brazilian regulation
set temporal restrictions that only slightly resemble those of Part 503 while Chilean and
Argentinean regulations adopt restrictions that combine concepts from both Part 503 and
Directive 86/278/EEC. The most temporal restrictions are set by Argentina while the longest
lasting are set by Brazil. Regarding vector attraction reduction, all regulations but Argentinean
consider mostly the same options set by Part 503. Sludge monitoring in all regulations follow
the model set by Part 503, however Mexican regulation requires a much laxer and less
frequent monitoring while the other three adopt a frequency mostly identical to Part 503. All
but Mexican regulation consider also soil monitoring under varying conditions and frequency.
Management and forbidden sites practices are not present in Mexican regulation. The less
stringent site restrictions are found in Brazilian regulation while Argentinean and Chilean
regulation focus mostly on avoiding high water content in soil and risk of surface water
contamination. All but Mexican regulation have also included other restrictions such as
maximum values for surface slope, maximum or minimum soil pH, minimum soil depth,
maximum permeability or sand content and minimum depth of water table. Brazilian,
Argentinean and Chilean regulations also consider minimum distances to different activities,
infrastructure and water bodies, with Chilean regulation considering the longest distances and
Brazilian regulation the most different restrictions.
Other European regulations considered mostly follow the model set by Directive
86/278/EEC. As stated by said Directive, no limits are allowed to go above it, however they do
differ on how far lower they are set, with Dutch regulation being the most stringent and
generally over an order of magnitude bellow low level limits set by Directive 86/278/EEC. As
stated by the 2001 European Commission report, this very stringent limits have derived in less
than 4% of the sludge produced being fit for land application in agriculture. Of the European
regulations considered, only French regulation contains limits for organic pollutants (PCB’s and
three PAH’s). Heavy metal limits in Spanish regulation are set according to soil pH while on
French regulation they depend on the type of agricultural land they are to be applied on. Limits
for heavy metals in soils prior to amendment differ between the three regulations, being
Dutch the most stringent in most cases and having a very detailed way of calculating the
specific limit for each case based on soil clay and organic matter contents. Limits for French
regulation are in between those set for high (>7) and low (<7) soil pH in Spanish regulation.
Only French regulation contains limits for pathogenic organisms and they are less stringent
than those set for Class A biosolids in Part 503. From this inclusion of limits to pathogenic
organisms, French regulation also establishes a class system for sludge as in Part 503 with
“General case” (Class B) and “Hygienized” (Class A) and thus also includes different time
restrictions for each case. Time restrictions set by all three regulations follow the model set by
Directive 86/278/EEC and the restrictions are identical except for the General case in French
regulation in which time restrictions are twice as long. There are no specific treatment options
detailed in any of the regulations and only a general requirement is put forth in each one. In
French and Dutch regulation it states that pathogenic most pathogenic organisms must be
killed by whichever treatment is given while Spanish regulation requires that the treatment
suffices to reduce “sanitary inconveniencies”. French and Spanish regulations also consider
that fermentability must be either reduced (Spanish) or completed or halted until land
application of sludge (French). Sludge monitoring practices from Spanish and Dutch regulation
are identical to those of Directive 86/278/EEC; however, Dutch regulation requires monitoring
of more parameters. French requirements for sludge monitoring are much more stringent in
their frequency, the highest being 48 times/year, and is based, as Part 503, on the amount of
sludge applied to land. Soil monitoring in Spanish and Dutch regulation is left to the
corresponding authorities criteria while French regulation states that it shall be done at least
once every 10 years. Regarding management practices, France and the Netherlands set limits
to the maximum amount of sludge that may be applied to land, regardless of its content of
pollutants; they also forbid application during seasons and under conditions which endanger
surface water bodies and in sites where slope is too high. However, regulation from the
Netherlands contains a series of detailed seasonal restrictions not present in any other
regulation analyzed. Finally, French regulation also considers various minimum distances to
different activities and infrastructures, which are based on the type of sludge used and the
slope of the surface on which it has been applied.
4.- Conclusions
The analytical technique employed is robust and provides good recoveries. The clean-
up procedure is very efficient, allowing for very well defined peaks with a low level of noise,
despite the complexity of the sample. The high level of interference removal can be partly
appreciated by the almost complete removal of color in the samples after clean-up. A key step
for obtaining a low baseline was the addition of activated copper to avoid fouling of the
electron emission source, the detector and the column. Further analysis should be carried out
to provide more insight into the nature of temporal tendencies in PBDE’s concentration in
Mexican sewage sludge and samples of the influent and effluent of the WWTP to provide
information of the source and removal efficiency. The very high content of PBDE’s in Mexican
sludge, compared to Shanghainese sludge, requires further information on the sources of the
wastewater being treated at Cerro de la Estrella WWTP.
While Directive 86/278/EEC is very basic in what it considers, other regulations from
de European Union have expanded on it significantly, including different limits according to soil
pH and the particular activities being developed in the site which is to be amended. Though
the aim of Directive 86/278/EEC is to encourage the use of sludge in agriculture while
protecting soil from heavy metal, excessively stringent regulations from member states have
also led to a very reduced amount of sludge being fit for land amendment, requiring other
methods of disposal such as incineration, which presents its own challenges. In America,
though there is no all-encompassing organism that includes and regulates all countries such as
the EU, many countries adopt the regulations of the United States. While this may be
beneficial in some cases given the extensive regulation they provide, it also means that, unless
precaution is exercised, shortcomings present in Part 503 may find their way to other
countries as well. In this respect, Brazilian regulation contains several additions to Part 503
while maintaining the core elements and revising some of the limits to heavy metals. Likewise,
Chilean regulation maintains most of the original content of Part 503 while providing much
more stringent limits for heavy metals, in some cases bellow those of Directive 86/278/EEC.