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Hannover Milieu- en Veiligheidstechniek B.V.




                                               An overview
                                                 HMVT INNOVATIVE AND EFFECTIVE
                                                 Twenty years of experience in soil,
                                                 water and air remediation
2
Table of contents
Profile	 	        	       	   	   	   	   	   	   	   4

Physical remediation                                  6

Biological remediation                                9

Chemical	remediation	 	       	   	   	   	   	   	   14

Test facilities                                       19

Purification	installations	   	   	   	   	   	   	   21

Want to know more?                                    23




                                                           3
‘Where traditional methods are inadequate or
          too costly, HMVT tackles soil challenges
              with specialist in-situ remediation’




4
Profile

A floating crust of diesel under a former industrial site, polluted groundwater or hydrocarbon contamination in the
inner city. When contamination is complex, you want to keep the risk to humans and the environment as small as
possible. At the same time you want building development to carry on. This demands the right response. Where
traditional methods are inadequate or too costly, HMVT tackles soil challenges with specialist in-situ remediation.
We have been doing this since 1988. Efficiently, lean and saving costs.



In-situ techniques                                                        •	 chemical	degradation	of	pollutants
In-situ remediation removes subsoil and residual contamination            •	 monitoring	the	stability	of	degradation	processes	(monitoring	of	
on site. The advantages? Profound contamination and large-                natural degradation/stability is a passive remediation technology
scale plume areas are more accessible and there is no need to             that requires no active/physical remediation. This remediation
demolish buildings. Soil remediation no longer stands in the way of       method will not be discussed in this document
constructing new buildings or infrastructure. We can deploy various
in-situ techniques depending on the type and magnitude of the             For optimum results, we combine various remediation techniques
pollution.                                                                where necessary within our remediation solutions. Our R & D team is
                                                                          continually researching innovations that can deal with contamination
Why HMVT?                                                                 even	more	efficiently.	We	work	with	students,	research	laboratories	
You are looking for an experienced remediator who can solve soil          and consultancies on this.
problems	smartly	and	efficiently.	A	company	which	will	tackle	
every soil problem individually and which uses state of the art           Besides soil remediation, HMVT has also gained a lot of experience
remediation technology. Public authorities, industrial concerns,          with	many	types	of	air	and	(waste)	water	treatment	in	the	past	20	
property developers and large-scale remediators know our strengths.       years,	both	within	and	outside	the	remediation	market.	As	a	result,	
HMVT has been involved in hundreds of projects at home and                HMVT not only has the necessary expertise to design air and waste
abroad since 1988, ranging from soil surveys to pilot projects, from      water treatment systems, but also has available a very broad range
complex decontaminations to after-care programmes, both small             of	measuring	tools	and	purification	equipment.
and massive. We have applied virtually every method and we have
experience of almost every pollution scenario. Not only do we             The following pages give a detailed explanation of the various
implement projects but we also offer advice and design.                   remediation techniques and other services which HMVT can offer.


Our company
HMVT employs experienced environmental scientists and
technicians. On average, our employees have been working in this
field	for	ten	years.	Quality	and	safety	are	at	the	core	of	our	company	
strategy. We work in teams, put together on the basis of knowledge
and experience. We don’t impose sections or other barriers between
our staff. Our staff consciously exchange practical experiences and
are trained in-house in our specialised professional area.


How we operate
Remediation is always a custom job. Besides that, we have also
found that the social and other costs of soil remediation should not
be excessive. That is why we aim to achieve remediation goals that
are	feasible	and	use	resources	and	energy	as	efficiently	as	possible.	
A	specialist	team	is	allocated	to	each	project.	This	team	draws	up	an	
action plan for each soil contamination problem and then designs,
constructs and maintains the necessary remediation installations.


Remediation techniques
HMVT is an all-round, in-situ soil remediator which uses the following
treatment methods:
•	 physical	removal	of	pollutants	
•	 biological	degradation	of	pollutants                                                 HMVT innovative and effective in-situ remediation




                                                                                                                                                 5
‘Contamination is extracted from
    the subsoil and treated above ground
              using various technologies’




6
Physical remediation

Physical remediation technology is understood to consist mainly of
methods by which contamination is extracted from the subsoil and
treated above ground. We apply the following physical techniques:


1.	 soil	vapour	extraction	(bioventing)	
2. various types of groundwater extraction
    - dewatering by vacuum drainage
    - gravity drainage
    - deep well drainage
	 -	re-infiltration	by	percolation
3.	 Multi	Phase	Extraction	(MPE)




Figure 1: Bioventing system




1. Soil vapour extraction                                                 Applicability
Soil	vapour	extraction	(SVE)	is	a	technology	that	takes	out	air	in	the	   For a large part, the porosity of the subsoil will determine the
subsoil from the unsaturated area by means of vertical extraction         applicability of bioventing. Bioventing can be applied in naturally
filters	or	horizontal	drains.	The	purpose	can	be	both	to	evaporate	       unsaturated,	moderately	porous	ground,	fine	sand	and	loamy	soils.	
volatile pollutants and to stimulate biological degradation by            As	regards	contamination,	this	technology	can	be	applied	to	the	
injecting additional oxygen into the ground by means of the induced       removal	of	volatile	compounds	which	have	a	Henri	coefficient	
air,	a	method	known	as	bioventing	(EPA,	1995).	                           exceeding	0.01	or	a	vapour	pressure	exceeding	approx.	0.7	mbar.			


Nutrients are often also injected when using this technique to            Professional practice
give nature a helping hand. Figure 2 is a representation of this          1.	Nijlen,	Belgium	(project	value	EUR	130,000):	Combination	of	
technology.                                                               air sparging, bioventing and groundwater extraction. Remediation
                                                                          resulted	in	a	reduction	of	the	polluting	chemical	cocktail	(styrene,	
                                                                          cresol,	phthalates,	isopropylbenzene	and	btex)	down	to	below	the	
                                                                          post-remediation value.
                                                                          2.	 Mechelen,	Belgium	(project	value	EUR	95,000):	Combination	of	
                                                                          air sparging, bioventing and groundwater extraction. Remediation
                                                                          of MTBE, volatile aromatics and mineral oils to below the post-
                                                                          remediation value imposed by the authorities.




Figure 2: high vacuum bioventing system

                                                                                                                                                  7
2. Groundwater extraction
                                                                                             Groundwater extraction is a perfect technology for
                                                                                             extracting	polluted	groundwater	(see	figure	3).	It	is	moreover	
                                                                                             used as an auxiliary method for biological and chemical
                                                                                             remediations. When nutrients or oxidants are injected into
                                                                                             the	ground	(reinfiltration),	groundwater	extraction	helps	to	
                                                                                             disperse these throughout the soil substrates. Groundwater
                                                                                             extraction includes gravity drainage, vacuum drainage and/
                                                                                             or	deep	well	reinfiltration.



    Figure 3: Gravitational pumping




    3. 3.     Multi phase extraction (MPE)
    A	third	method	for	extracting	groundwater	is	multi	phase	
    extraction. In this method a mixture of air, water and/or oil/
    oil products in the crust is extracted from the top layer of
    the	groundwater.	Figure	4	shows	a	diagram	of	MPE.	It	is	of	the	
    utmost importance in MPE to specify the scope of the water
    and	air	purification	installation	properly.	By	carrying	out	an	
    oil characterisation, it is possible to determine beforehand
    in	which	phase	(air	or	water)	the	oil	components	can	be	most	
    effectively	extracted	and	purified.	It	is	often	also	important	to	
    take additional measures because of the high concentrations
    of	contaminants	(e.g.	LEL	meter).

                                                                         Figure 4: Multiple phase extraction




    Applicability
    Top and subsoils often consist of layers with different
    porosities. The degree to which the porosity of these
    layers differs and the thickness of these layers determine
    the	heterogeneity	of	an	area	of	ground.	A	high	degree	of	
    heterogeneity negatively impacts the effectiveness of the
    transport	flow.	


    The	air	or	groundwater	often	flows	through	the	layers	with	
    higher	porosity,	whereas	these	can	hardly	flow	through	the	
    less porous layers. There are various ways substances can
    be transported through the soil. Figure 6 gives a summary
    of these methods. We often encounter situations in the soil
    remediation business where the contamination is adsorbed
    into	the	soil	matrix	(including	clay	minerals	and	organic	
    substances).	This	results	in	a	certain	equilibrium	between	the	
    contamination that is dissolved in the groundwater and the
    pollution adsorbed into the soil matrix.                             Figure 5: impression photo remediation installation at a large oildepot




8
Figure 6: Different forms of substance transport




This	is	expressed	in	the	distribution	coefficient	Kd.	It	is	essential	to	   Referentie HMVT
factor in both when calculating the load. Because bodies of water           1.	 Antwerp,	Belgium	(project	value	>	EUR	2,000,000):	Crust	layer	
are usually in motion, there are two processes taking place, namely         remediation	on	a	large	scale	with	more	than	600	remediation	filters.	
adsorption where pollution transforms from the water phase to               A	floating	crust	of	more	than	1,500	m3	was	removed.
the	adsorbed	state	(often	at	the	front)	and	retardation	where	the	
pollution transforms from the adsorbed state to the water phase.            2.	 Antwerp,	Belgium	(project	value	EUR	280,000):	Combination	of	
This latter phenomenon makes the front of the concentration move            crust remediation with groundwater extraction, bioventing and air
more slowly than the actual water body. This is also known as               sparging.	The	floating	crust	was	completely	removed.
delayed	flow.		
                                                                            3.	 Dendermonde,	Belgium	(project	value	EUR	92,000):	Removal	
                                                                            of	floating	crust	with	Multi	Phase	Extraction.	Crust	was	completely	
                                                                            removed thus achieving the remediation objectives.




                                                                                                                                                    9
‘Biological degradation is stimulated by
      optimising the conditions under which
                         degradation occurs’




10
Biological remediations

Biological remediation stimulates the degradation of contaminants. Biological degradation is stimulated by optimising
the conditions under which degradation occurs. The redox conditions (oxidation reduction) are crucial to this process.
If anaerobic conditions are desirable, for instance when tetrachloroethene (PCE) and trichloroethene (TCE) degrade,
a sustainably degradable substrate is added. The degradation of the substrate activates the naturally present electron
acceptors and helps to reduce the contamination. If there is too little natural substrate for reductive degrading to take
place, inserting additional substrate is the logical measure to take in this case. In the case of aerobic degradation, for
instance in the degradation of BTEX and oil, oxygen will be added. This can be done by injecting air or pure oxygen or
injecting substances which increase the level of oxygen. Any further stimulation is done by optimising the management
of nutrients.




                                                                      Compressed air injection (air sparging)
                                                                      Sparging air means injecting air under pressure using a compressor
                                                                      into the subsoil below the groundwater level. This method involves
                                                                      placing	a	grid	of	filters	(covering	the	surface)	below	the	water	table	
                                                                      level. This technique is used to evaporate the contamination from
                                                                      the	groundwater	(in-situ	stripping)	and	to	introduce	oxygen	into	the	
                                                                      polluted groundwater. This stimulates the naturally occurring aerobic
                                                                      degrading process.




Figure 7: manifold with 20 connections for largescale
substrate injection



HMVT has technologies at its disposal which stimulate both aerobic
and anaerobic degradation. Designing and monitoring degradation
processes forms part of our activities. In some cases natural
degradation	is	such	that	monitoring	is	sufficient.	


We apply the following methods:
1.	Aerobic	degradation:	injection	of	donor	oxygen
2.	Anaerobic	degradation:	injection	of	carbon	source
                                                                      Figure 8: principal biosparging and influence

Our	experts	can	find	out	whether	contamination	can	be	degraded	
by aerobic or anaerobic means. Biological techniques can offer an
affordable option as a biological protective screen in large plume    The	distance	between	the	filters	to	be	emplaced	depends	largely	on	
areas.                                                                the	impact	area	of	the	injected	air.	A	reasonable	primary	estimate	
                                                                      of this distance can be made by applying the principle that is
1. Aerobic degradation                                                illustrated	in	figure	8.	However,	specific	soil	characteristics	such	as	
Stimulated aerobic degradation is performed by introducing            the	type	of	subsoil	and	its	porosity	will	influence	the	impact	area	
oxygen and/or nutrients. This can be done with methods that use       to	a	great	extent.	We	advise	that	a	trial	is	carried	out	first	before	a	
compressed	air	injection	(CAI)	or	sparging,	soil	vapour	extraction	   full-scale system is installed. The necessary parameters can then be
(SVE)	and/or	direct	injection.                                        determined during the trials.




                                                                                                                                                 11
Applicability                                                             Applicability
     Sparging is suitable for the treatment of a saturated area, during        Contamination which is aerobically and biologically degradable
     which the unsaturated area is treated at the same time. When              can be remediated with the help of this technology. It has to be
     applying sparging for stripping, the released air is always captured in   said	that	oil	pollution	with	a	chain	length	exceeding	C30	is	very	
     the unsaturated area and removed under controlled conditions. The         difficult	to	remediate	using	this	technology.	Any	NAPL	strata	must	
     most crucial parameters that determine whether sparging is feasible       be removed prior to the remediation because these will prevent any
     are the porosity of the subsoil, the ground strata structure and the      remediation.
     extent of the volatility of the contamination.
                                                                               Heterogeneous soil structures can have a negative impact on the
     Professional practice                                                     remediation period and the result of the remediation because
     1.	 Vilvoorde,	Belgium	(project	value	EUR	800,000):	Combination	of	       less	permeable	layers	do	not	permit	an	efficient	flow	of	air.	
     Multi Phase Extraction, sparging and bioventing. Chlorohydrocarbon        Heterogeneity could also change the impact area to a large
     contamination was remediated by means of air sparging down to             extent.	A	field	trial	will	provide	more	certainty	in	this	regard.	The	
     below the value imposed by the Belgian authorities. Bioventing            permeability of a homogeneous soil stratum with poor porosity could
     ensured that the vapours released in the sparging process were            potentially be increased with the application of a fracturing process.
     extracted.
     2.	 Oosterhout,	The	Netherlands	(project	value	EUR	200,000):	             Professional practice
     Combination of chemical oxidation with bioventing and air sparging.       1.	 Antwerp,	Belgium	(project	value	EUR	200,000):	A	combination	
     The volatile aromatics and mineral oil contamination present in           of technologies arrived at values below the post-remediation value
     the plume area were reduced to below the post-remediation value           for volatile aromatics and mineral oils. Zero contamination has
     by means of sparging. The combination of chemical oxidation and           now been measured at several spots. The biological degradation
     sparging	resulted	in	reduction	of	the	load	by	more	than	90%.              conditions were at an optimum.
                                                                               2.	 Bilthoven,	The	Netherlands	(project	value	EUR	205,000):	
     Bioventing (soil vapour extraction)                                       Combination of air sparging with nutrient injection. The mineral oil
     The method of extracting air from the soil known as bioventing            and BTEX contamination found in the groundwater was remediated
     treats	the	unsaturated	zone	by	creating	a	vacuum	in	the	subsoil.	         and	certified	by	the	competent	authorities.
     This causes air in the soil to be refreshed with the ambient air.         3.	 Amsterdam,	The	Netherlands	(project	value	EUR	95,000):	Air	
     This change of air introduces oxygen into the soil which stimulates       sparging for the biological degrading of volatile aromatics and
     the biological aerobic activities of the micro-organisms. If there        mineral oil contamination.
     are volatile air pollutants present, vaporisation can take place
     simultaneously, which extracts any contaminated air that needs to
     be decontaminated. The amount of air to be extracted is determined        2. Anaerobic degradation
     by the quantity and degradability of the substance. The vacuum            Contamination can also be degraded under anaerobic conditions by
     required will be determined by the permeability of the substrate.         means of reductive processes. In contrast to oxidative degradation
                                                                               by means of bioventing and air sparging, the primary method is not
     Subsoil	air	can	be	extracted	via	vertical	filters.	If	there	are	any	      the application of an electron acceptor but the application of an
     buildings present, drains can be installed with the help of a             electron	donor	(substrate)	using	the	injection	method.	There	are	
     directional rotary well-sinking drill or high pressure drillings at an    many different ways to introduce substrates into the soil and there
     angle underneath the buildings in order to enable the directional         are many organic substances that are suitable as a substrate.
     extraction of air.
                                                                               Biological	degrading	of	VOCl	contaminants	(including	the	degreasing	
                                                                               substances	tetrachloroethene	(PCE)	and	trichloroethene	(TCE)	
                                                                               is possible in the right redox conditions and in the presence of
                                                                               substrate	(DOC).	A	micro-organism	uses	a	different	substance	(the	
                                                                               substrate)	as	food	and	breaks	down	the	chlorated	hydrocarbons	in	
                                                                               the process.


                                                                               The contamination is broken down to a harmless ethene in several
                                                                               steps. For example, contamination due to PCE and TCE but also the
                                                                               degradation products CIS and VC can be degraded anaerobically.
                                                                               Figure	10	shows	this	process.	


                                                                               ENNA injection (shock load)
                                                                               HMVT	selects	the	substrate	on	the	basis	of	the	specific	site	situation.	
                                                                               We frequently inject slow-release soya-based electron donor, which
                                                                               was	developed	by	our	own	R&D	section.	ENNA(Enhanced	Natural	
                                                                               Attenuation).	With	the	ENNA	method,	a	durable	substrate	is	injected	
                                                                               into the ground as shock-load. When using more common substrates
     Figure 9: subsoil tubing for bioventing system                            such as molasses, several injection booster sessions will be required
                                                                               for	sustained	stimulation	of	degradation.	The	ENNA	substrate	is	




12
•	We	are	able	to	inject	large	quantities	–	on	average	20	to	40	
                                                                            m3	per	day	–	with	our	newly	developed	‘biostimulator’.	Figure	
                                                                            11 gives an impression of the biostimulator. The container on
                                                                            the left has three holding tanks and the container on the right
                                                                            has mixing and injection tanks.

                                                                            Applicability
                                                                            Stimulated reductive attenuation is in principle suitable for
                                                                            all organic pollutants that can be converted reductively.
                                                                            In practice however its application is largely limited to
                                                                            chlorohydrocarbons and a few particular pollutants such as HCH
                                                                            and	chlorobenzene.	The	redox	conditions	in	the	groundwater	
                                                                            provide an important precondition for the success of stimulated
                                                                            reductive	dechlorination.	Under	anaerobic	conditions	where	
                                                                            a complete breakdown into harmless end products occurs
                                                                            naturally, successful remediation is much more likely than in a
                                                                            situation with aerobic conditions. Besides the electron donor,
                                                                            there may be other limiting factors, such as the availability of
                                                                            the contamination in the source area for example, or indeed
                                                                            the absence of suitable bacteria. If need be, we can inject
                                                                            supplementary bacteria.
Figure 10: principal biological degradation with ENNA




mixed on site and consists of an emulsion with extremely small
particles	(2	to	10	µm)	which	can	be	pressed	into	the	pores	of	the	
subsoils. The substrate is a mixture of soya and various agents,
which ensures that the nutrients will be released slowly over an
extended	period	(slow	release).	This	enables	the	bacteria	to	break	
down the contamination in the soil over a period of a few years up
to	a	maximum	of	five	years,	depending	on	the	other	characteristics	
of the soil. This is biological attenuation. The technology can be
applied	to	both	the	source	and	the	plume	area.	ENNA	can	also	be	
used as a biological screen to contain contamination. Compared to
other substrates that are often used such as lactates, protamylasses,
nutrolases	and	molasses,	ENNA	offers	the	following	advantages:
                                                                            Figure 11: the biostimulator
•	A	fine	emulsion	is	prepared	which	closely	resembles	milk.	This	can	
be easily injected to a considerable depth in the ground. The small
particles	(2	tot	10	µm)	easily	spread	and	penetrate	into	the	soil	          Professional practice
matrix.                                                                     1.	Dordrecht,	The	Netherlands	(project	value	EUR	73,000):	
•	Over	time,	the	substrate	reverts	gradually	to	a	biological	state;	        groundwater	extraction	and	infiltration	of	groundwater	
•	A	huge	amount	of	substrate	is	injected	all	at	the	same	time,	             with biological stimulants: By pumping groundwater to the
therefore	one	single	injection	is	sufficient	in	principle;	                 surface,	providing	a	substrate	and	reinfiltrating	this	mixture,	
•	ENNA	is	relatively	inexpensive;	                                          we successfully remediated a large plume area by means of
•	There	is	hardly	any	acidification	with	ENNA	such	as	occurs	with,	         anaerobic breakdown.
for	example,	lactates	and	molasses.	A	low	pH	as	a	consequence	of	           2.	Zwolle,	The	Netherlands	(project	value	EUR	700,000):	
acidification	has	a	negative	impact	on	biological	breakdown;                chemical oxidation in combination with stimulated breakdown.
•	Because	of	the	slow-release	effect,	the	conditions	for	biological	        Chemical oxidation removed a large part of the VOCl source.
activity remain very favourable and constant for a long time.               Biological breakdown followed successful stimulation after the
•	Contaminants	lose	their	mobility:	VOCl	contaminants	dissolve	             injection	of	ENNA,	developed	by	ourselves.	Save	for	1	level	
better	in	soya	oil	than	in	groundwater	by	a	factor	of	1200	times.	          indicator, the concentrations dwindled to below the post-
A	shift	takes	place:	the	contaminants	dissolve	into	the	substrate	          remediation value.
during the water and soil phases. The degree of contamination in the        3.	Veghel,	The	Netherlands	(project	value	EUR	350,000):	
groundwater decreases very quickly at the location of the substrate         stimulated	breakdown	of	VOCl	contamination	with	ENNA.	
injection because the pollutants dissolve into the substrate. This          Emplacement of bio-screen with injection of long-lasting
simultaneously creates an optimum mixture of the substrate and the          ENNA	carbon	source.	The	pollutants	in	the	plume	area,	which	
pollutant.	This	effect	is	particularly	apparent	in	residual	and	purified	   extends a few hundred metres, were stopped by three bio-
products.                                                                   screens.



                                                                                                                                               13
‘A technology that has proven itself in
        recent years is chemical oxidation’




14
Chemical remediations

There are two distinct types of chemical remediation: chemical oxidation (1) and chemical reduction (2).


A technology which has proven itself in recent years is chemical oxidation. This remediation technology yields very
high efficiencies in a short period of time. This technique is often applied particularly to core areas with high pollutant
concentrations. Depending on the local contamination situation, HMVT applies the following chemical oxidation
tehniques:


- chemical oxidation using hydrogen peroxide (Fenton’s reagent)
- chemical oxidation using ‘Enhanced’ Fenton’s
- chemical oxidation using permanganate
- chemical oxidation using activated persulphate


The correct application depends on the local circumstances and also on the applicability in combination with other
remediation methods.



It	may	happen	that	the	risk	of	mobile	pollutants	spreading	(e.g.	        A	large	number	of	pollutants	can	be	broken	down	using	ISCO,	
heavy	metals)	cannot	be	reversed	or	is	very	hard	to	stem	by	using	       depending on which pollutants the oxidising agent can deal with.
extractive, biological or other chemical remediation techniques. One     Table 1 gives a summary of which oxidation agents can remove certain
solution can be to immobilise the contamination, a technique also        pollutants.	Chemicals	have	been	arranged	from	vigorous	(top)	to	less	
known	as	‘stabilisation’.	These	techniques	come	under	the	heading	       active	(bottom).	Less	frequently	occurring	contaminations	which	
of	‘chemical	remediations’	because	stabilisation	is	a	(bio)chemical	     could potentially be remediated by ISCO have not been included in
reaction where the contamination reacts with a substrate that is         the	overview.	A	feasibility	test	by	the	HMVT	specialist	test	laboratory	
introduced, rendering it immobile. You can read more about this          could resolve this question.
under	the	heading	‘2.	Chemical	reduction’.
                                                                         Fenton’s reagent
                                                                         HMVT applies traditional Fenton’s Reagent. Fenton’s Reagent consists
                                                                         of	hydrogen	peroxide	as	oxidator	and	iron	(2+)	as	catalyst.	If	applied	
                                                                         correctly,	this	forms	the	extremely	reactive	hydroxyl	radical	(OH•).	
                                                                         The reaction equation is as follows:


                                                                         H2O2	+	Fe2+	 Fe3+	+	OH-	+	OH•


                                                                         These radicals are highly reactive and oxidise the most organic
                                                                         compounds, which releases a lot of reaction heat. Hydrogen
                                                                         peroxide is not a stable compound and breaks down into water and
                                                                         oxygen within a few days. This makes the reaction period in the
                                                                         ground quite short. On the other hand, no reaction products are
Figure 12: injectorhead                                                  generated which could lead to problems. The Fenton reaction is
                                                                         only effective at a low pH level between 2 and 6. The ideal pH level
                                                                         is	at	4	to	5	because	Fe2+ remains stable at low pH levels and does
1. Chemical oxidation                                                    not entirely deposit as iron oxide or hydroxide under the aerobic
During	in-situ	chemical	oxidation	(ISCO),	a	strong	oxidation	agent	in	   conditions created.
the form of a solid substance is diluted in water or injected into the
soil together with air. When the oxidation agent comes into contact      The	ground	is	first	made	‘oxidation	ready’in	the	process	used	by	HMVT.	
with the contamination in the ground, the pollutants are broken          This	is	done	by	lowering	the	pH	of	the	soil	to	between	3.5	and	4	while	
down	by	a	chemical	route	-	oxidisation	–	into	harmless	compounds	        at the same time introducing iron in the form of iron sulphate. One
which include water and carbon dioxide. Several oxidation agents         problem in this process can be the large buffer capacity of the ground,
are used in the soil remediation sector, where the contamination         for example because of a high calcium content.
breaks down indirectly via very highly oxidising small particles or
the contamination breaks down directly with the oxidation agents,        After	the	ground	has	been	prepared	for	oxidation,	the	hydrogen	
depending on the oxidation agent.                                        peroxide is injected into the ground. The hydrogen peroxide is injected

                                                                                                                                                    15
Oxidant                                    Pollution situation                            Can be applied to                             Cannot be applied to
         Fenton’s reagent and Enhanced              source area - may or may                       (chloro)ethenes,	                             weathered/heavy fraction
         Fenton’s reagent                           not contain pure product,                      (chloro)ethanes,	                             mineral oil, higher alkanes,
                                                    high groundwater levels                        BTEX, light fraction mineral                  heavy	fraction	PAH,	PCB,
                                                                                                   oil	and	PAH,	free	and	complex	
                                                                                                   cyanides, phenols, phthalates,
                                                                                                   MTBE, THF
         Ozone/peroxide                             source area - may or may                       (chloro)ethenes,	                             heavy	fraction	PAH2,
                                                    not contain pure product1,                     (chloro)alkanes,	                             PCB	2),	complex	cyanides
                                                    high groundwater levels in                     mineral oil, BTEX,
                                                    the plume area                                 lighter fraction
                                                                                                   PAH,	free	cyanides,	phenols,	
                                                                                                   phtha-lates, MTBE
         Persulfate                                 source area - may or may                       (chloro)ethenes,	                             heavy	fraction	PAH,	PCB
                                                    not contain pure product,                      (chloro)alkanes,	
                                                    high groundwater levels                        BTEX,	lighter	fraction	PAH,	
                                                                                                   phenols, phthalates, MTBE
         Ozone                                      source area - may or may                       (chloro)ethenes,	mineral	oil3,                (chloro)alkanes,	heavy	
                                                    not contain pure product,                      BTEX,	lighter	fraction	PAH,	free	             fraction	PAH,	PCB,	complex	
                                                    high groundwater levels in                     cyanides, phenols, phthalates,                cyanides
                                                    plume area                                     MTBE
         Permanganate                               source area - may or may                       chloroethenes, TEX4, phenols                  benzene,	(chloro)alkanes,	
                                                    not contain pure product,                                                                    mineral	oil,	PAH,	PCB,	cyanides
                                                    high groundwater levels


     Table 1: Overview table
     1
       According to the patent holder, not enough projects have been completed in the Netherlands to warrant application in soil that contains pure product.
     2
       According to the patent holder, breakdown does occur, but no practical examples from outside of the United States are known.
     3
       Mineral oil is not fully broken down into water and carbon dioxide, but into smaller hydrocarbon chains.
     4
       Permanganate cannot be applied in benzene contaminations, but it can be applied in the case of ethyl benzene, toluene and xylene(s).




     in	concentrations	of	between	5	and	15%	peroxide.	During	the	injection	                           •	 the	pH	is	not	reduced;	this	is	advantageous	if	the	next	step	involves	
     of the hydrogen peroxide the concentrations of hydrogen peroxide, the                            biological	breakdown;
     temperature,	pH,	Ec,	oxygen	level,	iron	II,	pressures,	yield	per	filter	and	                     •	 this	can	also	be	used	for	soils	with	a	high	buffering	capacity,	such	as	
     redox are all measured on the ground. Everything is aimed at keeping the                         chalky	soils;
     process under control.                                                                           •	 the	iron	becomes	available	gradually;	the	Fenton	reaction	therefore	
                                                                                                      happens more gradually and the Fenton’s Reagent continues to be
                                                                                                      effective for a longer period.


                                                                                                      In addition to using Fenton’s Reagent, HMVT is also experienced in the
                                                                                                      applications of permanganate and activated persulphate.


                                                                                                      Applicability
                                                                                                      ISCO can be deployed in a source area of the contamination but also
                                                                                                      in the rest of the plume area. The decision whether to enlist a given
                                                                                                      oxidation medium in a source or plume area depends on the location
                                                                                                      of	the	contamination	in	the	ground,	whether	there	is	any	purified	
                                                                                                      product, the period of time allowed for remediation and the cost.
                                                                                                      Some oxidation agents are too expensive to deploy where there are
                                                                                                      low contaminant concentrations in a plume area. Table 1 lists the
                                                                                                      oxidation	agents	that	can	be	used	in	a	given	situation.	A	number	of	
                                                                                                      oxidation agents are used for remediating soil contamination.
     Figure 13: The mobile injection unit (ISCO)
                                                                                                      This technique is particularly suitable for well to moderately
                                                                                                      draining soils. If the ground is almost impervious, special application
                                                                                                      techniques such as fracturing can be deployed. Natural organic
     Enhanced Fenton’s                                                                                substances	(OS)	and/or	reduced	inorganic	compounds	such	as	Fe2+	can	
     HMVT also makes use of Enhanced Fenton’s Reagent. The catalyst iron                              dramatically increase the quantity of oxidants required: the so-called
     chelate is applied instead of acid and iron sulph ate in the Enhanced                            matrix requirement of the soil.
     Fenton procedure. This makes it unnecessary to lower the pH level to
     3.5. Compared to traditional Fenton’s Reagent, this has the following                            The application of permanganate should be avoided for soils with poor
     advantages:                                                                                      drainage.	Manganese	oxide	(MnO2¬)	is	created	in	the	reaction	with	



16
permanganate,	which	is	difficult	to	dissolve	and	forms	a	deposit.	This	    The	carbon	source	(soya	oil)	that	is	being	oxidised	releases	electrons;	
can cause blockages in the soil pores if there are high concentrations     oxidation of the carbon source with sulphate results in a sulphide
of	contamination,	for	example	purified	product	in	the	source	areas	        that will be reduced.
of the contamination.
                                                                           Professional practice
Professional practice                                                      Pilot	in	Nederweert,	The	Netherlands	(project	value	EUR	80,000):	
1.	 Ermelo,	The	Netherlands	(project	value	EUR	107,000):	Chemical	         Injection	with	carbon	source	(‘pump	&	treat’)	in	combination	
oxidation in combination with Multi Phase Extraction to remove             with	groundwater	extraction	of	heavy	metals,	including	zinc	
aircraft fuel. Combining these techniques caused a drop in                 contamination.	Further	dispersion	of	zinc	in	the	groundwater	was	
concentrations,	which	was	certified	by	the	competent	authorities.		        stopped	completely	thanks	to	successfully	stabilising	the	zinc.
2.	 Doetinchem,	The	Netherlands	(project	value	EUR	700,000):	
Chemical oxidation in combination with biological stimulation
(ENNA):	remediation	of	VOCl	contamination	with	chemical	oxidation	
led to a dramatic decline in the source concentrations, which
made stimulated biological breakdown possible. Following the
remediation, the location was declared suitable for the development
of new apartments.
3.	 Bergermeer,	The	Netherlands	(project	value	EUR	15,000):	
Chemical oxidation of volatile aromatics and mineral oils with an
effectiveness	of	more	than	90%.


2. Chemical reduction
In locations where other in-situ remediation technologies are not
able	either	to	break	down	contamination	(biological	stimulation	and	
chemical	oxidation)	or	to	extract	contamination	from	the	soil,	there	
is a third option for tackling the risks of mobile contaminations,
namely chemical reduction. HMVT applies two technologies in
particular which come under this heading, i.e. stabilisation when          Figure 14: Nano iron in a drop of oil

heavy	metals	are	present	and	injection	of	‘FENNA’	for	chemically	
pure	products,	including	VOCl).


Stabilisation                                                              ‘FENNA’
A	frequently	occurring	contamination	for	which	the	above	in-situ	          Chemical reduction is applied to locations where pure chemical
remediation technologies are inadequate, are heavy metals. For             products	are	found.	By	reducing	Fe	to	Fe2+	under	strongly	reduced	
example,	zinc	can	be	stabilised	by	means	of	sulphide.	Sulphide	makes	      conditions	(Redox	300),	PCE	can	be	converted	to	harmless	ethene	via	
a	deposit	with	zinc	in	the	form	of	zinc	sulphide	(ZnS).	The	prevailing	    TRI, CIS and VC. However, this technology is only effective if the iron
macro-chemical	conditions	such	as	redox	at	less	than	-150mV	and	           particles are extremely small, i.e. so-called nano particles between
acidity	level	at	pH	6	or	lower,	are	also	significant.	The	microbiology	    100	and	200	nm.	This	reaction	will	only	occur	on	the	surface	of	
at the location is also important because bacteria are the driving         the iron particle. The smaller the particle, the larger the relative
force behind the reduction of sulphate to sulphide. The following is a     surface.	This	technique	is	known	in	the	United	States	as	‘Nanoscale	
phased plan for the reduction processes that occur in the soil and on      Zero Valent Iron’ or NZVI for short.
which	the	stabilisation	of	zinc	is	based.	These	reactions	take	place	in	
the groundwater under anaerobic environmental conditions.                  The pollutants PCE and TRI dissolve considerably better in oily
                                                                           substances	than	in	water.	In	this	application	the	iron	0	nano	particles	
                                                                           are dissolved in a vegetable based soya oil. This oil is subsequently
step 1                                                                     injected	as	an	emulsion	(small	oil	droplets	measuring	just	a	few	µm).	 	
NO3-	+	H+	+	carbon	source	→				N2	+	H2O	+	CO2	      	                      After	the	oil	is	injected	into	the	ground,	the	contaminants	will	be	
reduction	of	nitrate	(NO3-)                                                concentrated in the oil droplets. The pollutant will then react with
                                                                           the	iron	0	nano	particles	in	the	oil	droplets.	
step 2
Fe3+	+	H+	+	carbon	source	→				Fe2+	+	H2O	+	CO2	 	                         After	the	iron	reaction	is	exhausted,	the	biological	breakdown	will	
reduction	of	iron	(3+)	(Fe3+)                                              take over and then the vegetable based soya oil will be used as the
                                                                           DOC source. HMVT uses the combination of chemical reduction with
step 3                                                                     0-value	iron	and	ENNA	for	applications	under	the	name	of	‘FENNA’.	
SO42−	+	carbon	source	→				HS−/H2S-	+	CO2	+	H2O	
reduction of sulphate


step 4
Fe2+/Zn2+	+	SO42-	+	carbon	source	→				FeS/ZnS	+	H2O		
zinc	deposit	(ISMP)




                                                                                                                                                      17
‘Thanks to our knowledge combined with supplementary
      tests, we are able to give a verdict on the remediation
          method and its feasibility for almost every case of
                                             contamination’




18
Test facilities

Detailed information about the soil, the groundwater and the
contamination are crucial for in-situ remediation. In some cases
previous investigations into drawing up remediation plans are not
sufficiently	complete	for	proposing	the	optimum	in-situ	remediation	
technology. For example, information may be missing that could give
an indication of the potential biological activities on site. This could
include the redox conditions, the iron content and/or the sulphate
content. If chemical oxidation is included, it will be necessary to
obtain an impression of the buffer capacity to be able to calculate
the chemical quantities to be applied.



                                                                           Figure 16: impression photo 2 HMVT lab




                                                                           Besides the laboratory tests which are needed to obtain
                                                                           supplementary	information	for	specific	projects,	the	lab	is	also	
                                                                           used within HMVT’s Research & Development section. Thanks to
                                                                           our knowledge combined with supplementary tests, we are able
                                                                           to give a verdict on the remediation method and its feasibility for
                                                                           almost every case of contamination. New techniques are developed
                                                                           year on year thus carrying on the tradition of innovation at HMVT.
                                                                           We are able to accomplish this partly thanks to our laboratories
Figure 15: impression photo HMVT lab
                                                                           and	by	carrying	out	pilot	field	trials.	Besides	research	into	ground	
                                                                           remediation	we	also	carry	out	tests	to	find	the	most	suitable	
HMVT has its own laboratory facilities with all the necessary              purification	methods	for	air	and	water.	You	will	find	a	series	of	new	
equipment	to	carry	out	these	tests.	A	field	sample	of	water	and/           technologies developed by HMVT summarised under the heading
or soil is taken and analysed in several tests under laboratory            ‘Professional	practice’.
conditions. The following is a list of experiments and tests:
                                                                           Professional practice
For extractive remediations:                                               1. Development of new chemical oxidation techniques
•	 Permeability	test                                                       2.	 Development	of	the	sustainable	substrate	ENNA	(ENhanced	
•	 Contaminant	analysis                                                    Natural	Attenuation)
                                                                           3. Development of several substrate compounds for biological
For biological stimulation:                                                breakdown of VOCl
•	 Contaminant	analysis                                                    4.	 Feasibility	tests	for	biological	breakdown	of	contamination	with	
•	 Buffering	capacity                                                      various substrates
•	 Attenuation	test	(aerobic	and	anaerobic)                                5.	 Jar	tests	for	the	optimisation	of	water	purification	methods,	e.g.	
•	 Laboratory	analysis	(iron,	sulphate,	DOC,	etc.)                         iron removal
                                                                           6.	 Dispersion	behaviour	of	ENNA	in	the	soil
For chemical oxidation:
•	 Contaminant	analysis
•	 Determine	the	buffering	capacity
•	 Determine	the	matrix	requirement
•	 Attenuation	test




                                                                                                                                                     19
‘HMVT has multiple technologies available which
               it builds in-house for purifying various
                   contaminated air and water flows’




20
Purification	plant

It	is	often	necessary	to	purify	air	and	water	flows	when	extracting	
polluted	groundwater	and/or	air	from	the	soil	(see	section	‘Physical	
remediation’).	This	depends,	among	other	things,	on	the	discharge	
and emission standards for water and air.


HMVT has several technologies available which it builds in-house for
purifying	various	contaminated	air	and	water	flows.	A	summary	of	
these is given below.


Water purification using:
•	 Strip	towers
•	 Plate	aerator
•	 Sand	filtration
•	 Oil	water	separator	(OWAS)
•	 ‘Wet’	active	carbon
•	 Ion	exchange


Air purification using:
•	 Catalytic	burning
•	 ‘Dry’	active	carbon
•	 Corona	pulsed	plasma	(industrial	air	cleansing)
•	 Oxicator
•	 Biofilter	(biobed)


The	design	and	spatial	assessment	of	the	different	purification	
installations	depends	very	much	on	the	flow	to	be	treated	and	the	
extracted contamination.


The	photographs	below	show	various	purification	installations.




                                                                        Figure 19: Air stripping tower




                         Figure 17: Catalytic burning                   Figure 18: Sand filtration




                                                                                                         21
22
Want to know more?

HMVT	would	very	much	like	to	meet	the	challenge	of	finding	the	
optimum solution to your soil, water or air problem. Our strength?
Know-how,	years	of	experience	and	an	innovative	outlook.	Would	
you like to know more about the possibilities we offer in the area
of in-situ remediation? Our consultants are always willing to answer
your	queries	and	provide	you	with	more	information.	Also	visit	
www.hmvt.eu	for	more	information	on	our	specific	products	and	
services.



Hannover Milieu- en Veiligheidstechniek B.V.
P.O.	Box	174
6710	BD	Ede	
T	NL	+	31	(0)318	-	624	624
T	BE	+	32	(0)3	-	609	55	30
E info@hmvt.nl
www.hmvt.nl




                                                                       23
HMVT: in situ remediation

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HMVT: in situ remediation

  • 1. Hannover Milieu- en Veiligheidstechniek B.V. An overview HMVT INNOVATIVE AND EFFECTIVE Twenty years of experience in soil, water and air remediation
  • 2. 2
  • 3. Table of contents Profile 4 Physical remediation 6 Biological remediation 9 Chemical remediation 14 Test facilities 19 Purification installations 21 Want to know more? 23 3
  • 4. ‘Where traditional methods are inadequate or too costly, HMVT tackles soil challenges with specialist in-situ remediation’ 4
  • 5. Profile A floating crust of diesel under a former industrial site, polluted groundwater or hydrocarbon contamination in the inner city. When contamination is complex, you want to keep the risk to humans and the environment as small as possible. At the same time you want building development to carry on. This demands the right response. Where traditional methods are inadequate or too costly, HMVT tackles soil challenges with specialist in-situ remediation. We have been doing this since 1988. Efficiently, lean and saving costs. In-situ techniques • chemical degradation of pollutants In-situ remediation removes subsoil and residual contamination • monitoring the stability of degradation processes (monitoring of on site. The advantages? Profound contamination and large- natural degradation/stability is a passive remediation technology scale plume areas are more accessible and there is no need to that requires no active/physical remediation. This remediation demolish buildings. Soil remediation no longer stands in the way of method will not be discussed in this document constructing new buildings or infrastructure. We can deploy various in-situ techniques depending on the type and magnitude of the For optimum results, we combine various remediation techniques pollution. where necessary within our remediation solutions. Our R & D team is continually researching innovations that can deal with contamination Why HMVT? even more efficiently. We work with students, research laboratories You are looking for an experienced remediator who can solve soil and consultancies on this. problems smartly and efficiently. A company which will tackle every soil problem individually and which uses state of the art Besides soil remediation, HMVT has also gained a lot of experience remediation technology. Public authorities, industrial concerns, with many types of air and (waste) water treatment in the past 20 property developers and large-scale remediators know our strengths. years, both within and outside the remediation market. As a result, HMVT has been involved in hundreds of projects at home and HMVT not only has the necessary expertise to design air and waste abroad since 1988, ranging from soil surveys to pilot projects, from water treatment systems, but also has available a very broad range complex decontaminations to after-care programmes, both small of measuring tools and purification equipment. and massive. We have applied virtually every method and we have experience of almost every pollution scenario. Not only do we The following pages give a detailed explanation of the various implement projects but we also offer advice and design. remediation techniques and other services which HMVT can offer. Our company HMVT employs experienced environmental scientists and technicians. On average, our employees have been working in this field for ten years. Quality and safety are at the core of our company strategy. We work in teams, put together on the basis of knowledge and experience. We don’t impose sections or other barriers between our staff. Our staff consciously exchange practical experiences and are trained in-house in our specialised professional area. How we operate Remediation is always a custom job. Besides that, we have also found that the social and other costs of soil remediation should not be excessive. That is why we aim to achieve remediation goals that are feasible and use resources and energy as efficiently as possible. A specialist team is allocated to each project. This team draws up an action plan for each soil contamination problem and then designs, constructs and maintains the necessary remediation installations. Remediation techniques HMVT is an all-round, in-situ soil remediator which uses the following treatment methods: • physical removal of pollutants • biological degradation of pollutants HMVT innovative and effective in-situ remediation 5
  • 6. ‘Contamination is extracted from the subsoil and treated above ground using various technologies’ 6
  • 7. Physical remediation Physical remediation technology is understood to consist mainly of methods by which contamination is extracted from the subsoil and treated above ground. We apply the following physical techniques: 1. soil vapour extraction (bioventing) 2. various types of groundwater extraction - dewatering by vacuum drainage - gravity drainage - deep well drainage - re-infiltration by percolation 3. Multi Phase Extraction (MPE) Figure 1: Bioventing system 1. Soil vapour extraction Applicability Soil vapour extraction (SVE) is a technology that takes out air in the For a large part, the porosity of the subsoil will determine the subsoil from the unsaturated area by means of vertical extraction applicability of bioventing. Bioventing can be applied in naturally filters or horizontal drains. The purpose can be both to evaporate unsaturated, moderately porous ground, fine sand and loamy soils. volatile pollutants and to stimulate biological degradation by As regards contamination, this technology can be applied to the injecting additional oxygen into the ground by means of the induced removal of volatile compounds which have a Henri coefficient air, a method known as bioventing (EPA, 1995). exceeding 0.01 or a vapour pressure exceeding approx. 0.7 mbar. Nutrients are often also injected when using this technique to Professional practice give nature a helping hand. Figure 2 is a representation of this 1. Nijlen, Belgium (project value EUR 130,000): Combination of technology. air sparging, bioventing and groundwater extraction. Remediation resulted in a reduction of the polluting chemical cocktail (styrene, cresol, phthalates, isopropylbenzene and btex) down to below the post-remediation value. 2. Mechelen, Belgium (project value EUR 95,000): Combination of air sparging, bioventing and groundwater extraction. Remediation of MTBE, volatile aromatics and mineral oils to below the post- remediation value imposed by the authorities. Figure 2: high vacuum bioventing system 7
  • 8. 2. Groundwater extraction Groundwater extraction is a perfect technology for extracting polluted groundwater (see figure 3). It is moreover used as an auxiliary method for biological and chemical remediations. When nutrients or oxidants are injected into the ground (reinfiltration), groundwater extraction helps to disperse these throughout the soil substrates. Groundwater extraction includes gravity drainage, vacuum drainage and/ or deep well reinfiltration. Figure 3: Gravitational pumping 3. 3. Multi phase extraction (MPE) A third method for extracting groundwater is multi phase extraction. In this method a mixture of air, water and/or oil/ oil products in the crust is extracted from the top layer of the groundwater. Figure 4 shows a diagram of MPE. It is of the utmost importance in MPE to specify the scope of the water and air purification installation properly. By carrying out an oil characterisation, it is possible to determine beforehand in which phase (air or water) the oil components can be most effectively extracted and purified. It is often also important to take additional measures because of the high concentrations of contaminants (e.g. LEL meter). Figure 4: Multiple phase extraction Applicability Top and subsoils often consist of layers with different porosities. The degree to which the porosity of these layers differs and the thickness of these layers determine the heterogeneity of an area of ground. A high degree of heterogeneity negatively impacts the effectiveness of the transport flow. The air or groundwater often flows through the layers with higher porosity, whereas these can hardly flow through the less porous layers. There are various ways substances can be transported through the soil. Figure 6 gives a summary of these methods. We often encounter situations in the soil remediation business where the contamination is adsorbed into the soil matrix (including clay minerals and organic substances). This results in a certain equilibrium between the contamination that is dissolved in the groundwater and the pollution adsorbed into the soil matrix. Figure 5: impression photo remediation installation at a large oildepot 8
  • 9. Figure 6: Different forms of substance transport This is expressed in the distribution coefficient Kd. It is essential to Referentie HMVT factor in both when calculating the load. Because bodies of water 1. Antwerp, Belgium (project value > EUR 2,000,000): Crust layer are usually in motion, there are two processes taking place, namely remediation on a large scale with more than 600 remediation filters. adsorption where pollution transforms from the water phase to A floating crust of more than 1,500 m3 was removed. the adsorbed state (often at the front) and retardation where the pollution transforms from the adsorbed state to the water phase. 2. Antwerp, Belgium (project value EUR 280,000): Combination of This latter phenomenon makes the front of the concentration move crust remediation with groundwater extraction, bioventing and air more slowly than the actual water body. This is also known as sparging. The floating crust was completely removed. delayed flow. 3. Dendermonde, Belgium (project value EUR 92,000): Removal of floating crust with Multi Phase Extraction. Crust was completely removed thus achieving the remediation objectives. 9
  • 10. ‘Biological degradation is stimulated by optimising the conditions under which degradation occurs’ 10
  • 11. Biological remediations Biological remediation stimulates the degradation of contaminants. Biological degradation is stimulated by optimising the conditions under which degradation occurs. The redox conditions (oxidation reduction) are crucial to this process. If anaerobic conditions are desirable, for instance when tetrachloroethene (PCE) and trichloroethene (TCE) degrade, a sustainably degradable substrate is added. The degradation of the substrate activates the naturally present electron acceptors and helps to reduce the contamination. If there is too little natural substrate for reductive degrading to take place, inserting additional substrate is the logical measure to take in this case. In the case of aerobic degradation, for instance in the degradation of BTEX and oil, oxygen will be added. This can be done by injecting air or pure oxygen or injecting substances which increase the level of oxygen. Any further stimulation is done by optimising the management of nutrients. Compressed air injection (air sparging) Sparging air means injecting air under pressure using a compressor into the subsoil below the groundwater level. This method involves placing a grid of filters (covering the surface) below the water table level. This technique is used to evaporate the contamination from the groundwater (in-situ stripping) and to introduce oxygen into the polluted groundwater. This stimulates the naturally occurring aerobic degrading process. Figure 7: manifold with 20 connections for largescale substrate injection HMVT has technologies at its disposal which stimulate both aerobic and anaerobic degradation. Designing and monitoring degradation processes forms part of our activities. In some cases natural degradation is such that monitoring is sufficient. We apply the following methods: 1. Aerobic degradation: injection of donor oxygen 2. Anaerobic degradation: injection of carbon source Figure 8: principal biosparging and influence Our experts can find out whether contamination can be degraded by aerobic or anaerobic means. Biological techniques can offer an affordable option as a biological protective screen in large plume The distance between the filters to be emplaced depends largely on areas. the impact area of the injected air. A reasonable primary estimate of this distance can be made by applying the principle that is 1. Aerobic degradation illustrated in figure 8. However, specific soil characteristics such as Stimulated aerobic degradation is performed by introducing the type of subsoil and its porosity will influence the impact area oxygen and/or nutrients. This can be done with methods that use to a great extent. We advise that a trial is carried out first before a compressed air injection (CAI) or sparging, soil vapour extraction full-scale system is installed. The necessary parameters can then be (SVE) and/or direct injection. determined during the trials. 11
  • 12. Applicability Applicability Sparging is suitable for the treatment of a saturated area, during Contamination which is aerobically and biologically degradable which the unsaturated area is treated at the same time. When can be remediated with the help of this technology. It has to be applying sparging for stripping, the released air is always captured in said that oil pollution with a chain length exceeding C30 is very the unsaturated area and removed under controlled conditions. The difficult to remediate using this technology. Any NAPL strata must most crucial parameters that determine whether sparging is feasible be removed prior to the remediation because these will prevent any are the porosity of the subsoil, the ground strata structure and the remediation. extent of the volatility of the contamination. Heterogeneous soil structures can have a negative impact on the Professional practice remediation period and the result of the remediation because 1. Vilvoorde, Belgium (project value EUR 800,000): Combination of less permeable layers do not permit an efficient flow of air. Multi Phase Extraction, sparging and bioventing. Chlorohydrocarbon Heterogeneity could also change the impact area to a large contamination was remediated by means of air sparging down to extent. A field trial will provide more certainty in this regard. The below the value imposed by the Belgian authorities. Bioventing permeability of a homogeneous soil stratum with poor porosity could ensured that the vapours released in the sparging process were potentially be increased with the application of a fracturing process. extracted. 2. Oosterhout, The Netherlands (project value EUR 200,000): Professional practice Combination of chemical oxidation with bioventing and air sparging. 1. Antwerp, Belgium (project value EUR 200,000): A combination The volatile aromatics and mineral oil contamination present in of technologies arrived at values below the post-remediation value the plume area were reduced to below the post-remediation value for volatile aromatics and mineral oils. Zero contamination has by means of sparging. The combination of chemical oxidation and now been measured at several spots. The biological degradation sparging resulted in reduction of the load by more than 90%. conditions were at an optimum. 2. Bilthoven, The Netherlands (project value EUR 205,000): Bioventing (soil vapour extraction) Combination of air sparging with nutrient injection. The mineral oil The method of extracting air from the soil known as bioventing and BTEX contamination found in the groundwater was remediated treats the unsaturated zone by creating a vacuum in the subsoil. and certified by the competent authorities. This causes air in the soil to be refreshed with the ambient air. 3. Amsterdam, The Netherlands (project value EUR 95,000): Air This change of air introduces oxygen into the soil which stimulates sparging for the biological degrading of volatile aromatics and the biological aerobic activities of the micro-organisms. If there mineral oil contamination. are volatile air pollutants present, vaporisation can take place simultaneously, which extracts any contaminated air that needs to be decontaminated. The amount of air to be extracted is determined 2. Anaerobic degradation by the quantity and degradability of the substance. The vacuum Contamination can also be degraded under anaerobic conditions by required will be determined by the permeability of the substrate. means of reductive processes. In contrast to oxidative degradation by means of bioventing and air sparging, the primary method is not Subsoil air can be extracted via vertical filters. If there are any the application of an electron acceptor but the application of an buildings present, drains can be installed with the help of a electron donor (substrate) using the injection method. There are directional rotary well-sinking drill or high pressure drillings at an many different ways to introduce substrates into the soil and there angle underneath the buildings in order to enable the directional are many organic substances that are suitable as a substrate. extraction of air. Biological degrading of VOCl contaminants (including the degreasing substances tetrachloroethene (PCE) and trichloroethene (TCE) is possible in the right redox conditions and in the presence of substrate (DOC). A micro-organism uses a different substance (the substrate) as food and breaks down the chlorated hydrocarbons in the process. The contamination is broken down to a harmless ethene in several steps. For example, contamination due to PCE and TCE but also the degradation products CIS and VC can be degraded anaerobically. Figure 10 shows this process. ENNA injection (shock load) HMVT selects the substrate on the basis of the specific site situation. We frequently inject slow-release soya-based electron donor, which was developed by our own R&D section. ENNA(Enhanced Natural Attenuation). With the ENNA method, a durable substrate is injected into the ground as shock-load. When using more common substrates Figure 9: subsoil tubing for bioventing system such as molasses, several injection booster sessions will be required for sustained stimulation of degradation. The ENNA substrate is 12
  • 13. • We are able to inject large quantities – on average 20 to 40 m3 per day – with our newly developed ‘biostimulator’. Figure 11 gives an impression of the biostimulator. The container on the left has three holding tanks and the container on the right has mixing and injection tanks. Applicability Stimulated reductive attenuation is in principle suitable for all organic pollutants that can be converted reductively. In practice however its application is largely limited to chlorohydrocarbons and a few particular pollutants such as HCH and chlorobenzene. The redox conditions in the groundwater provide an important precondition for the success of stimulated reductive dechlorination. Under anaerobic conditions where a complete breakdown into harmless end products occurs naturally, successful remediation is much more likely than in a situation with aerobic conditions. Besides the electron donor, there may be other limiting factors, such as the availability of the contamination in the source area for example, or indeed the absence of suitable bacteria. If need be, we can inject supplementary bacteria. Figure 10: principal biological degradation with ENNA mixed on site and consists of an emulsion with extremely small particles (2 to 10 µm) which can be pressed into the pores of the subsoils. The substrate is a mixture of soya and various agents, which ensures that the nutrients will be released slowly over an extended period (slow release). This enables the bacteria to break down the contamination in the soil over a period of a few years up to a maximum of five years, depending on the other characteristics of the soil. This is biological attenuation. The technology can be applied to both the source and the plume area. ENNA can also be used as a biological screen to contain contamination. Compared to other substrates that are often used such as lactates, protamylasses, nutrolases and molasses, ENNA offers the following advantages: Figure 11: the biostimulator • A fine emulsion is prepared which closely resembles milk. This can be easily injected to a considerable depth in the ground. The small particles (2 tot 10 µm) easily spread and penetrate into the soil Professional practice matrix. 1. Dordrecht, The Netherlands (project value EUR 73,000): • Over time, the substrate reverts gradually to a biological state; groundwater extraction and infiltration of groundwater • A huge amount of substrate is injected all at the same time, with biological stimulants: By pumping groundwater to the therefore one single injection is sufficient in principle; surface, providing a substrate and reinfiltrating this mixture, • ENNA is relatively inexpensive; we successfully remediated a large plume area by means of • There is hardly any acidification with ENNA such as occurs with, anaerobic breakdown. for example, lactates and molasses. A low pH as a consequence of 2. Zwolle, The Netherlands (project value EUR 700,000): acidification has a negative impact on biological breakdown; chemical oxidation in combination with stimulated breakdown. • Because of the slow-release effect, the conditions for biological Chemical oxidation removed a large part of the VOCl source. activity remain very favourable and constant for a long time. Biological breakdown followed successful stimulation after the • Contaminants lose their mobility: VOCl contaminants dissolve injection of ENNA, developed by ourselves. Save for 1 level better in soya oil than in groundwater by a factor of 1200 times. indicator, the concentrations dwindled to below the post- A shift takes place: the contaminants dissolve into the substrate remediation value. during the water and soil phases. The degree of contamination in the 3. Veghel, The Netherlands (project value EUR 350,000): groundwater decreases very quickly at the location of the substrate stimulated breakdown of VOCl contamination with ENNA. injection because the pollutants dissolve into the substrate. This Emplacement of bio-screen with injection of long-lasting simultaneously creates an optimum mixture of the substrate and the ENNA carbon source. The pollutants in the plume area, which pollutant. This effect is particularly apparent in residual and purified extends a few hundred metres, were stopped by three bio- products. screens. 13
  • 14. ‘A technology that has proven itself in recent years is chemical oxidation’ 14
  • 15. Chemical remediations There are two distinct types of chemical remediation: chemical oxidation (1) and chemical reduction (2). A technology which has proven itself in recent years is chemical oxidation. This remediation technology yields very high efficiencies in a short period of time. This technique is often applied particularly to core areas with high pollutant concentrations. Depending on the local contamination situation, HMVT applies the following chemical oxidation tehniques: - chemical oxidation using hydrogen peroxide (Fenton’s reagent) - chemical oxidation using ‘Enhanced’ Fenton’s - chemical oxidation using permanganate - chemical oxidation using activated persulphate The correct application depends on the local circumstances and also on the applicability in combination with other remediation methods. It may happen that the risk of mobile pollutants spreading (e.g. A large number of pollutants can be broken down using ISCO, heavy metals) cannot be reversed or is very hard to stem by using depending on which pollutants the oxidising agent can deal with. extractive, biological or other chemical remediation techniques. One Table 1 gives a summary of which oxidation agents can remove certain solution can be to immobilise the contamination, a technique also pollutants. Chemicals have been arranged from vigorous (top) to less known as ‘stabilisation’. These techniques come under the heading active (bottom). Less frequently occurring contaminations which of ‘chemical remediations’ because stabilisation is a (bio)chemical could potentially be remediated by ISCO have not been included in reaction where the contamination reacts with a substrate that is the overview. A feasibility test by the HMVT specialist test laboratory introduced, rendering it immobile. You can read more about this could resolve this question. under the heading ‘2. Chemical reduction’. Fenton’s reagent HMVT applies traditional Fenton’s Reagent. Fenton’s Reagent consists of hydrogen peroxide as oxidator and iron (2+) as catalyst. If applied correctly, this forms the extremely reactive hydroxyl radical (OH•). The reaction equation is as follows: H2O2 + Fe2+  Fe3+ + OH- + OH• These radicals are highly reactive and oxidise the most organic compounds, which releases a lot of reaction heat. Hydrogen peroxide is not a stable compound and breaks down into water and oxygen within a few days. This makes the reaction period in the ground quite short. On the other hand, no reaction products are Figure 12: injectorhead generated which could lead to problems. The Fenton reaction is only effective at a low pH level between 2 and 6. The ideal pH level is at 4 to 5 because Fe2+ remains stable at low pH levels and does 1. Chemical oxidation not entirely deposit as iron oxide or hydroxide under the aerobic During in-situ chemical oxidation (ISCO), a strong oxidation agent in conditions created. the form of a solid substance is diluted in water or injected into the soil together with air. When the oxidation agent comes into contact The ground is first made ‘oxidation ready’in the process used by HMVT. with the contamination in the ground, the pollutants are broken This is done by lowering the pH of the soil to between 3.5 and 4 while down by a chemical route - oxidisation – into harmless compounds at the same time introducing iron in the form of iron sulphate. One which include water and carbon dioxide. Several oxidation agents problem in this process can be the large buffer capacity of the ground, are used in the soil remediation sector, where the contamination for example because of a high calcium content. breaks down indirectly via very highly oxidising small particles or the contamination breaks down directly with the oxidation agents, After the ground has been prepared for oxidation, the hydrogen depending on the oxidation agent. peroxide is injected into the ground. The hydrogen peroxide is injected 15
  • 16. Oxidant Pollution situation Can be applied to Cannot be applied to Fenton’s reagent and Enhanced source area - may or may (chloro)ethenes, weathered/heavy fraction Fenton’s reagent not contain pure product, (chloro)ethanes, mineral oil, higher alkanes, high groundwater levels BTEX, light fraction mineral heavy fraction PAH, PCB, oil and PAH, free and complex cyanides, phenols, phthalates, MTBE, THF Ozone/peroxide source area - may or may (chloro)ethenes, heavy fraction PAH2, not contain pure product1, (chloro)alkanes, PCB 2), complex cyanides high groundwater levels in mineral oil, BTEX, the plume area lighter fraction PAH, free cyanides, phenols, phtha-lates, MTBE Persulfate source area - may or may (chloro)ethenes, heavy fraction PAH, PCB not contain pure product, (chloro)alkanes, high groundwater levels BTEX, lighter fraction PAH, phenols, phthalates, MTBE Ozone source area - may or may (chloro)ethenes, mineral oil3, (chloro)alkanes, heavy not contain pure product, BTEX, lighter fraction PAH, free fraction PAH, PCB, complex high groundwater levels in cyanides, phenols, phthalates, cyanides plume area MTBE Permanganate source area - may or may chloroethenes, TEX4, phenols benzene, (chloro)alkanes, not contain pure product, mineral oil, PAH, PCB, cyanides high groundwater levels Table 1: Overview table 1 According to the patent holder, not enough projects have been completed in the Netherlands to warrant application in soil that contains pure product. 2 According to the patent holder, breakdown does occur, but no practical examples from outside of the United States are known. 3 Mineral oil is not fully broken down into water and carbon dioxide, but into smaller hydrocarbon chains. 4 Permanganate cannot be applied in benzene contaminations, but it can be applied in the case of ethyl benzene, toluene and xylene(s). in concentrations of between 5 and 15% peroxide. During the injection • the pH is not reduced; this is advantageous if the next step involves of the hydrogen peroxide the concentrations of hydrogen peroxide, the biological breakdown; temperature, pH, Ec, oxygen level, iron II, pressures, yield per filter and • this can also be used for soils with a high buffering capacity, such as redox are all measured on the ground. Everything is aimed at keeping the chalky soils; process under control. • the iron becomes available gradually; the Fenton reaction therefore happens more gradually and the Fenton’s Reagent continues to be effective for a longer period. In addition to using Fenton’s Reagent, HMVT is also experienced in the applications of permanganate and activated persulphate. Applicability ISCO can be deployed in a source area of the contamination but also in the rest of the plume area. The decision whether to enlist a given oxidation medium in a source or plume area depends on the location of the contamination in the ground, whether there is any purified product, the period of time allowed for remediation and the cost. Some oxidation agents are too expensive to deploy where there are low contaminant concentrations in a plume area. Table 1 lists the oxidation agents that can be used in a given situation. A number of oxidation agents are used for remediating soil contamination. Figure 13: The mobile injection unit (ISCO) This technique is particularly suitable for well to moderately draining soils. If the ground is almost impervious, special application techniques such as fracturing can be deployed. Natural organic Enhanced Fenton’s substances (OS) and/or reduced inorganic compounds such as Fe2+ can HMVT also makes use of Enhanced Fenton’s Reagent. The catalyst iron dramatically increase the quantity of oxidants required: the so-called chelate is applied instead of acid and iron sulph ate in the Enhanced matrix requirement of the soil. Fenton procedure. This makes it unnecessary to lower the pH level to 3.5. Compared to traditional Fenton’s Reagent, this has the following The application of permanganate should be avoided for soils with poor advantages: drainage. Manganese oxide (MnO2¬) is created in the reaction with 16
  • 17. permanganate, which is difficult to dissolve and forms a deposit. This The carbon source (soya oil) that is being oxidised releases electrons; can cause blockages in the soil pores if there are high concentrations oxidation of the carbon source with sulphate results in a sulphide of contamination, for example purified product in the source areas that will be reduced. of the contamination. Professional practice Professional practice Pilot in Nederweert, The Netherlands (project value EUR 80,000): 1. Ermelo, The Netherlands (project value EUR 107,000): Chemical Injection with carbon source (‘pump & treat’) in combination oxidation in combination with Multi Phase Extraction to remove with groundwater extraction of heavy metals, including zinc aircraft fuel. Combining these techniques caused a drop in contamination. Further dispersion of zinc in the groundwater was concentrations, which was certified by the competent authorities. stopped completely thanks to successfully stabilising the zinc. 2. Doetinchem, The Netherlands (project value EUR 700,000): Chemical oxidation in combination with biological stimulation (ENNA): remediation of VOCl contamination with chemical oxidation led to a dramatic decline in the source concentrations, which made stimulated biological breakdown possible. Following the remediation, the location was declared suitable for the development of new apartments. 3. Bergermeer, The Netherlands (project value EUR 15,000): Chemical oxidation of volatile aromatics and mineral oils with an effectiveness of more than 90%. 2. Chemical reduction In locations where other in-situ remediation technologies are not able either to break down contamination (biological stimulation and chemical oxidation) or to extract contamination from the soil, there is a third option for tackling the risks of mobile contaminations, namely chemical reduction. HMVT applies two technologies in particular which come under this heading, i.e. stabilisation when Figure 14: Nano iron in a drop of oil heavy metals are present and injection of ‘FENNA’ for chemically pure products, including VOCl). Stabilisation ‘FENNA’ A frequently occurring contamination for which the above in-situ Chemical reduction is applied to locations where pure chemical remediation technologies are inadequate, are heavy metals. For products are found. By reducing Fe to Fe2+ under strongly reduced example, zinc can be stabilised by means of sulphide. Sulphide makes conditions (Redox 300), PCE can be converted to harmless ethene via a deposit with zinc in the form of zinc sulphide (ZnS). The prevailing TRI, CIS and VC. However, this technology is only effective if the iron macro-chemical conditions such as redox at less than -150mV and particles are extremely small, i.e. so-called nano particles between acidity level at pH 6 or lower, are also significant. The microbiology 100 and 200 nm. This reaction will only occur on the surface of at the location is also important because bacteria are the driving the iron particle. The smaller the particle, the larger the relative force behind the reduction of sulphate to sulphide. The following is a surface. This technique is known in the United States as ‘Nanoscale phased plan for the reduction processes that occur in the soil and on Zero Valent Iron’ or NZVI for short. which the stabilisation of zinc is based. These reactions take place in the groundwater under anaerobic environmental conditions. The pollutants PCE and TRI dissolve considerably better in oily substances than in water. In this application the iron 0 nano particles are dissolved in a vegetable based soya oil. This oil is subsequently step 1 injected as an emulsion (small oil droplets measuring just a few µm). NO3- + H+ + carbon source → N2 + H2O + CO2 After the oil is injected into the ground, the contaminants will be reduction of nitrate (NO3-) concentrated in the oil droplets. The pollutant will then react with the iron 0 nano particles in the oil droplets. step 2 Fe3+ + H+ + carbon source → Fe2+ + H2O + CO2 After the iron reaction is exhausted, the biological breakdown will reduction of iron (3+) (Fe3+) take over and then the vegetable based soya oil will be used as the DOC source. HMVT uses the combination of chemical reduction with step 3 0-value iron and ENNA for applications under the name of ‘FENNA’. SO42− + carbon source → HS−/H2S- + CO2 + H2O reduction of sulphate step 4 Fe2+/Zn2+ + SO42- + carbon source → FeS/ZnS + H2O zinc deposit (ISMP) 17
  • 18. ‘Thanks to our knowledge combined with supplementary tests, we are able to give a verdict on the remediation method and its feasibility for almost every case of contamination’ 18
  • 19. Test facilities Detailed information about the soil, the groundwater and the contamination are crucial for in-situ remediation. In some cases previous investigations into drawing up remediation plans are not sufficiently complete for proposing the optimum in-situ remediation technology. For example, information may be missing that could give an indication of the potential biological activities on site. This could include the redox conditions, the iron content and/or the sulphate content. If chemical oxidation is included, it will be necessary to obtain an impression of the buffer capacity to be able to calculate the chemical quantities to be applied. Figure 16: impression photo 2 HMVT lab Besides the laboratory tests which are needed to obtain supplementary information for specific projects, the lab is also used within HMVT’s Research & Development section. Thanks to our knowledge combined with supplementary tests, we are able to give a verdict on the remediation method and its feasibility for almost every case of contamination. New techniques are developed year on year thus carrying on the tradition of innovation at HMVT. We are able to accomplish this partly thanks to our laboratories Figure 15: impression photo HMVT lab and by carrying out pilot field trials. Besides research into ground remediation we also carry out tests to find the most suitable HMVT has its own laboratory facilities with all the necessary purification methods for air and water. You will find a series of new equipment to carry out these tests. A field sample of water and/ technologies developed by HMVT summarised under the heading or soil is taken and analysed in several tests under laboratory ‘Professional practice’. conditions. The following is a list of experiments and tests: Professional practice For extractive remediations: 1. Development of new chemical oxidation techniques • Permeability test 2. Development of the sustainable substrate ENNA (ENhanced • Contaminant analysis Natural Attenuation) 3. Development of several substrate compounds for biological For biological stimulation: breakdown of VOCl • Contaminant analysis 4. Feasibility tests for biological breakdown of contamination with • Buffering capacity various substrates • Attenuation test (aerobic and anaerobic) 5. Jar tests for the optimisation of water purification methods, e.g. • Laboratory analysis (iron, sulphate, DOC, etc.) iron removal 6. Dispersion behaviour of ENNA in the soil For chemical oxidation: • Contaminant analysis • Determine the buffering capacity • Determine the matrix requirement • Attenuation test 19
  • 20. ‘HMVT has multiple technologies available which it builds in-house for purifying various contaminated air and water flows’ 20
  • 21. Purification plant It is often necessary to purify air and water flows when extracting polluted groundwater and/or air from the soil (see section ‘Physical remediation’). This depends, among other things, on the discharge and emission standards for water and air. HMVT has several technologies available which it builds in-house for purifying various contaminated air and water flows. A summary of these is given below. Water purification using: • Strip towers • Plate aerator • Sand filtration • Oil water separator (OWAS) • ‘Wet’ active carbon • Ion exchange Air purification using: • Catalytic burning • ‘Dry’ active carbon • Corona pulsed plasma (industrial air cleansing) • Oxicator • Biofilter (biobed) The design and spatial assessment of the different purification installations depends very much on the flow to be treated and the extracted contamination. The photographs below show various purification installations. Figure 19: Air stripping tower Figure 17: Catalytic burning Figure 18: Sand filtration 21
  • 22. 22
  • 23. Want to know more? HMVT would very much like to meet the challenge of finding the optimum solution to your soil, water or air problem. Our strength? Know-how, years of experience and an innovative outlook. Would you like to know more about the possibilities we offer in the area of in-situ remediation? Our consultants are always willing to answer your queries and provide you with more information. Also visit www.hmvt.eu for more information on our specific products and services. Hannover Milieu- en Veiligheidstechniek B.V. P.O. Box 174 6710 BD Ede T NL + 31 (0)318 - 624 624 T BE + 32 (0)3 - 609 55 30 E info@hmvt.nl www.hmvt.nl 23